Proceedings of the 10th International Conference on Environmental Science and Technology

Kos island, Greece, 5 – 7 September 2007

OPTIMISATION AND EVALUATION OF THE COAGULATION BEHAVIOUR OF

THE MODIFIED INORGANIC POLYMERIC COAGULANT, POLYFERRIC
SILICATE SULPHATE (PFSiS)

A.I. ZOUBOULIS* and P.A. MOUSSAS

Division of Chemical Technology, Department of Chemistry,

Aristotle University of Thessaloniki, Greece

ABSTRACT

Polyferric Silicate sulphate (PFSiS) is a modified pre-polymerised inorganic coagulant.

PFSiS is prepared with hydroxylation of the mixture of Fe2(SO4)3 and fresh polysilicic acid
under different Fe/Si and OH/Fe molar ratios.
The aim of this paper is to determine the optimum experimental conditions under which
the new coagulant shows the highest coagulation efficiency and to evaluate the
coagulant’s performance in comparison with other iron-based coagulants. Therefore, the
effect of coagulant dosage, pH and concentration of polyelectrolyte on removing the
turbidity from simulated surface water was investigated. The extent of aggregation and
the dynamics of flocculation were studied using a continuous optical flocculation monitor
(PDA 2000).
Finally, the coagulation performance of the PFSiS, considering the reduction of turbidity
of kaolin-humic acid suspension, was evaluated in comparison with other iron-based
coagulants.

Keywords: Coagulation, inorganic polymeric flocculants, polyferric silicate sulphate

1. INTRODUCTION

A new kind of coagulants/flocculants is the inorganic polymeric flocculants (IPFs) such as

the polyferric sulphate (PFS) and polyferric chloride (PFC) (Jiang and Graham [1]; Jiang
and Graham [2]; Chang and Wang [3]; Leprince et al [4]). The IPFs are pre-hydrolysed
coagulants, which are prepared by partially neutralisation of iron salts. During the
neutralisation, several polymerisation reactions occur resulting in the formation of various
polymeric species of iron. However, despite the fact that their efficiency is significantly
higher than that of the conventional coagulants, it is still much lower than that of the
organic polymeric coagulants (Tang and Shi [5]). The basic prerequisites for an effective
coagulant are the charge-neutralisation capacity and the bridge-aggregation ability. There
are two ways for improving the efficiency of the IPFs; either by increasing the proportion
of the polymeric species in their original composition or by adding other components to
produce new composite coagulants. Concerning the second method, the additive
frequently used is polysilicic acid (PSiA), which carries a negative charge. The main goals
of adding such a modifier are to increase the molecular size and enhance the
aggregating ability of the coagulant as well as increasing their stability and durability
(Tang and Shi [5], Wang and Tang [6]).
A characteristic example of a modified IPF is the Polyferric Silicate Sulphate (PFSiS).
PFSiS is prepared with hydroxylation of the mixture of Fe2(SO4)3 and fresh polysilicic acid
under different Fe/Si and r = OH/Fe molar ratios.
In this paper, the coagulating behaviour of PFSiS is investigated. In particular, the effect
of coagulant dosage, of Fe/Si molar ratio, pH and concentration of polyelectrolyte on

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removing the turbidity from simulated surface water was investigated. Moreover, the
coagulation dynamics were examined by means of an optical flocculation monitor
(Photometric Dispersion Analyser, PDA 2000). Finally, the coagulation performance of
the PFSiS, considering the reduction of turbidity of kaolin - humic acid suspension, was
evaluated in comparison with other iron-based coagulants.

2. MATERIALS AND METHODS

2.1 Preparation of PFSiS
PFSiS is prepared by mixing fresh polysilicic acid (PSiA) and iron salt (Fe2(SO4)3) and
then by partially neutralising the mixture with the addition of a base solution (NaHCO3).
Further details concerning the preparation method and the characterisation of the
coagulants can be found elsewhere (Zouboulis et al [7]).

2.2 Study of kinetics of the coagulation using of the Photometric Dispersion

Analyser (PDA)

The extent of aggregation, as well as the kinetics of coagulation was examined with the
aid of Photometric Dispersion Analyser (PDA 2000). The PDA instrument measures the
ratio R, which is directly related with the mean concentration and size of dispersed
particles. The ratio R curves derived from the PDA instrument has the typical form shown
in Figure 1 (Hopkins and Ducoste [8]).
The R curve can be divided into three parts: A) immediately after the coagulant addition
there is a small change in the R values. During this part, which is called “lag phase”, the
destabilisation of the particles takes place. B) Then, the linear growth region part follows,
where the collisions of previously destabilized particles result in aggregate formation. C)
Finally, in the equilibrium phase the value of the R remains relatively constant as the rate
of the formation and the breakage of flocs is rather equal. Generally, it can be concluded
that the higher R values imply bigger particles size and therefore, a better separation by
the application of subsequent sedimentation.

Figure 1: Schematic representation of the typical ratio R curve

2.3 Coagulation experiments

Kaolin – humic acid model suspension was used as the test suspension, dosed with the
appropriate amount of the coagulant. The concentration of the stock kaolin suspension
and of humic acid solution was 5 g/L, respectively. The test suspensions were prepared
by diluting the stock solutions with tap water to concentration of 5 mg/L of both kaolin and
humic acid. Table I summarises the typical properties of the kaolin-humic acid
suspension. The pH value of the test suspension was adjusted with dilute HCl solution or

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NaOH solution. An anionic polyacrylamide (product name: Magnafloc LT25, Ciba SC)
was used as a flocculant aid. The experimental conditions were the following: the initial
fast mixing time was set to 3 min at the paddle speed of 200 rpm to allow the particles to
be destabilized followed by the flocculation period (set to 30 min and with paddle speed
of 35 rpm) and the final sedimentation period, which lasts for 45 min. After that a
supernatant sample (100 ml) was withdrawn for further analysis. A typical method for
assessing the coagulation efficiency is to determine the reduction in the turbidity of the
test suspension.

Table I. Properties of the kaolin - humic acid suspension

z-potential Conductivity
pH NTU UV254
(mV) (mS/cm)
Kaolin–Humic acid
7.3 10 -32 0.60 0.116
suspension

3 RESULTS AND DISCUSSION

3.1 Study of the kinetics of the coagulation process using the PDA

3.1.1 Effect of mixing speed (or velocity gradient G (s-1)) in the kinetics of
coagulation
The effect of speed during the fast mixing period on the coagulation process is shown in Figure
2. The mixing speed is expressed in rpm, as well as in velocity gradient units G (s-1).The test
suspension is kaolin-humic acid suspension (5 mg/L) and the coagulant used is PFSiS
(Fe/Si = 0.5, OH/Fe =0.5, 4 mg/L as Fe).

3.0

2.5

2.0
ratio

1.5

180s
1.0 -1
140rpm,159s
-1
160rpm,200s
0.5 -1
180rpm,241s
-1
200rpm,282s
0.0
0 200 400 600 800 1000 1200 1400

time (sec)

Figure 2. Effect of fast mixing speed (or velocity gradient G (s-1)) in kaolin-humic acid
suspension (PFSiS, Fe/Si =0.5, 4 mg/L as Fe )

As shown in Figure 2, for the mixing speed of 200 rpm the lag phase is limited
highlighting that the formation of flocs occurs quickly. Additionally, the higher values of
ratio R after the equilibrium stage show that the formed flocs are bigger in size. For the
mixing speed of 180 rpm, the coagulation performance is similar to that of 200 rpm
although relatively worse in terms of the size of flocs and duration of lag phase. On the
contrary, for lower speeds, i.e. 140 and 160 rpm, the lag phase is more extended and
therefore the formation of flocs is delayed. Moreover, the values of ratio R are lower, as
the flocculation of suspended particles proceeds in a slower rate and the formed flocs are
smaller in size.

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3.1.2 Effect of mixing time in the kinetics of coagulation process
Figure 3 shows the effect of mixing time in the kinetics of coagulation process. The test
suspension was kaolin-humic acid suspension (5 mg/L) and the coagulant used was
PFSiS (Fe/Si = 0.5, OH/Fe =0.5, 4 mg/L as Fe). The speed in the fast mixing stage is 200
rpm, which found to be the optimum as shown in the previous section 3.1.1. The higher
values of ratio, which correspond to the bigger size of formed flocs, were achieved, when
the fast mixing time was 180s. It is worth noting that the lag phase in all cases is similar
and the fact that distinguishes the curves is the different R values during the slow mixing
period. It is suggested that the longer duration of the fast mixing period enables a better
particle destabilisation and consequently a quicker formation of bigger flocs.

4 .5

4 .0

3 .5

3 .0

2 .5
ratio

2 .0

1 .5
-1
2 00 rp m , 28 2 s
1 .0 60 s
90 s
0 .5 12 0s
18 0s
0 .0
0 200 400 600 800 1000 1200 1400

tim e (s e c )

Figure 3. Impact of time during the fast mixing period in kaolin-humic acid suspension
(PFSiS, Fe/Si =0.5, 4 mg/L as Fe )

3.1.3 Effect of pH in the kinetics of coagulation process

Figure 4 illustrates the effect of pH in the kinetics of coagulation process.

-1
2 0 0 rp m , 2 8 2 s , 1 8 0 s
pH 5
pH 6
4 .5 pH 7
pH 8
4 .0 pH 9

3 .5

3 .0

2 .5
ratio

2 .0

1 .5

1 .0

0 .5

0 .0
0 200 400 600 800 1000 1200 1400

tim e (s e c )

Figure 4. Effect of pH on the kinetics of coagulation process in a kaolin-humic acid

suspension. (PFSiS, Fe/Si =0.5, 4 mg/L as Fe)

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As shown in Fig.4, for a pH range of 6-9, there are no significant differences in the
coagulation performance. However, it is worth noting that for pH value 6, the formation of
flocs is quicker, while the high values of R ratio suggests that the flocculation proceeds in
a fast rate and the formed flocs are bigger in size and more stable. On the other hand, for
pH value 5, the lag phase is significantly extended resulting in a slow formation of flocs
which are smaller in size and not as stable as in the other cases.

3.2 Optimisation of coagulation process

3.2.1 Effect of PFSiS dosage and Fe/Si Molar ratio on coagulation performance
Figure 5 illustrates the effect of PFSiS dosage and of Fe/Si molar ratio on reducing the
turbidity of the test suspension. The test suspension was the kaolin-humic acid
suspension, whose properties are summarised in Table I. The polyelectrolyte used was
anionic polyacrylamide (product name: Magnafloc LT25, Ciba SC), for a dosage
corresponding to the 1/10th of the coagulant dosage.

5 .5 F e /S i = 1 .0 , O H /F e = 0 .5
5 .0 F e /S i = 1 .5 , O H /F e = 0 .5
F e /S i = 2 .0 , O H /F e = 0 .5
4 .5
Residual Turbidity (NTU)

F e /S i = 3 .0 , O H /F e = 0 .5
4 .0

3 .5

3 .0

2 .5

2 .0

1 .5

1 .0

0 .5

1 2 3 4 5 6

P F S iS D o s a g e (m g /L a s F e )

Figure 5. Effect of PFSiS dosage and Fe/Si molar ratio on coagulation performance

The results illustrate that the Fe/Si molar ratios 1.0 and 1.5 exhibit the best coagulation
performance. Generally, it can be suggested that the high Fe/Si molar ratios i.e.2.0, 3.0
have a detrimental effect on the coagulation performance and therefore excessive
coagulant’s dosages are required in order to improve the coagulation efficiency.
Additionally, a coagulant dose within the range of 3-4 mg/L exhibits the best turbidity
removal effect in all cases. When higher dosages were used, the coagulation
performance is compromised possibly due to the fact that high dosages restabilise the
particles.

3.2.2 Effect of pH on coagulation performance of PFSiS

Figure 6 shows the effect of pH on reducing the turbidity of the kaolin-humic acid test
suspension. The dosage of PFSiS was 4 mg/L as Fe (Fe/Si =1.0, 2.0, OH/Fe =0.5). The
polyelectrolyte used was anionic polyacrylamide (product name: Magnafloc LT25, Ciba
SC), for a dosage corresponding to the 1/10th of the coagulant dosage.

The results show that the coagulation performance of PFSiS is almost similar in the pH
range of 5-9. In lower pH, i.e pH =4, the coagulation efficiency is significantly decreased.
It can also be suggested that the Fe/Si molar ratio has no effect on producing a pH range
suitable for coagulation as in both cases the performance is very similar. These findings
are in total agreement with the conclusions drawn from the PDA experiments.

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 16

14
F e /S i = 1 .0 , O H /F e = 0 .5

Residual Turbidity (NTU)

12
F e /S i = 2 .0 , O H /F e = 0 .5
10

4 5 6 7 8 9

pH

Figure 6. Effect of pH on the coagulation performance of PFSiS

Figure 7 illustrates the relation of pH to the z-potential values of the flocs produced during
the aforementioned experiment.

15
F e /S i = 1 .0 , O H /F e = 0 .5
10
F e /S i = 2 .0 , O H /F e = 0 .5
5
z-potential (mV)

-5

-1 0

-1 5

-2 0

-2 5

4 5 6 7 8 9

pH

Figure 7. Effect of pH on the z-potential values of the formed flocs.

Figure 6 and 7 demonstrates that PFSiS is very efficient in removing the turbidity from the
kaolin-humic acid suspension, even when the flocs formed during the process are more
negatively charged i.e in pH 8 and 9. So, it can be suggested that the PFSiS is effective
in the aspect of bridge-formation due to the presence of silica in its composition.

3.2.3 Effect of polyelectrolyte dosage on coagulation performance of PFSiS

Figure 8 illustrates the effect of polyelectrolyte dosage on coagulation performance of
PFSiS. The test suspension was the kaolin-humic acid suspension and the dosage of
PFSiS (Fe/Si =1.0, 2.0, OH/Fe =0.5) was 4 mg/L as Fe.

As shown in Fig 8, the optimum polyelectrolyte concentration is in the range of 0.3 -0.4
mg/L, in other words, in a concentration equal to the 1/10th of the coagulant dosage.
Lower or higher dosages result in decreasing the coagulation efficiency due to the fact
that, in the former case, the polymeric species are not sufficient enough for adsorbing the

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particles and form aggregates and, in the latter case, excessive dosage of polyelectrolyte
added results in the isolation and restabilisation of the particles.
2 .4

2 .2 F e /S i = 1 .0 , O H /F e = 0 . 5
F e /S i = 2 .0 , O H /F e = 0 . 5
2 .0

Residual Turbidity (NTU) 1 .8

1 .6

1 .4

1 .2

1 .0

0 .8

0 .6
0 .2 0 .3 0 .4 0 .5 0 .6

P o ly e le c tr o ly te D o s a g e (A n io n ic ) (m g /L )

Figure 8. Effect of polyelectrolyte dosage on coagulation performance of PFSiS

3.2.4 Comparison between PFSiS and other iron-based coagulants

Figure 9 illustrates the comparative results between the PFSiS (Fe/Si =1.0, OH/Fe =0.5)
and other iron based coagulants, i.e. Polyferric sulphate (PFS) and ferric sulphate (FS).
The test suspension was the kaolin-humic acid suspension and an anionic
polyacrylamide (product name: Magnafloc LT25, Ciba SC) was used as a flocculant aid
for a dosage corresponding to the 1/10th of the coagulant dosage.
5 .0

4 .5 P F S iS
PFS
4 .0 FS
Residual Turbidity (NTU)

3 .5

3 .0

2 .5

2 .0

1 .5

1 .0

0 .5
1 2 3 4 5 6

P F S iS D o s a g e ( m g /L F e )

Figure 9. Comparison of coagulation performance between PFSiS, PFS and FS

The results demonstrate that the new coagulant, PFSiS, exhibits a significantly superior
coagulation performance under the specific experimental conditions compared with the
other iron-based coagulants.

4 CONCLUSIONS
Overall, this study show that PFSiS, as a new type of modified inorganic coagulant,
exhibits a superior coagulation performance compared with other iron-based coagulants.
PDA experiments enable the study of the process of coagulation and the determination of
the optimum conditions for the fast mixing period which are 200 rpm (282s-1) and 180s.
Coagulation experiments also illustrate that the Fe/Si molar ratio significantly affects the

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coagulation efficiency and that the PFSiS has similarly good performance in a pH range
of 5-9. Furthermore, a polyelectrolyte dosage equal to 1/10th of coagulant dosage is
required for achieving the highest efficiency. Finally, it is suggested that the PFSiS is
effective in the aspect of bridge-formation due to the presence of silica in its composition.

ACKNOWLEDGEMENTS
Thanks are due to the Greek Ministry of Education (YPEPTh) for funding this research
through the Pythagoras-II program. The present study was co-funded by European
Union, European Social Fund and National Funds.

5 REFERENCES
[1] Jiang, J-Q., Graham, N.J.D., (1998), “Pre-polymerised inorganic coagulants and phosphorus
removal by coagulation – a review”, Water SA. 24 (3), 237-244,
[2] Jiang, J-Q., Graham, N.J.D., (1998), “Preparation and characterisation of an optimal polyferric
sulphate (PFS) as a coagulant for water treatment” J.Chem. Technol. Biot. 73, 351-358,
[3] Chang, Q., Wang, H., (2002), “Preparation of PFS coagulant by sectionalised reactor”, J
Environ Sci. 14 (3), 345-350,
[4] Leprince, A., Flessinger, F., Bottero, JY., (1984) “Polymerised iron Chloride: An improved
inorganic coagulant”, J. Am. Water Works Assoc. 76, 93-97,
[5] Tang H., Shi B., “The characteristics of composite flocculants synthesised with inorganic
polyaluminum and organic polymers”, Chemical Water and Wastewater Treatment VII, IWA
Publishing, London, pp 17-28
[6] Wang D., Tang H., (2001) “Modified inorganic polymer flocculant-PFSi: Its preparation,
characterisation and coagulation behaviour“, Water research, 35(14), 3418-3428
[7] Zouboulis A.I., Moussas P.A., (November 2006), “Polyferric Silicate Sulphate (PFSiS):
Preparation, characterisation and coagulation behaviour”, Proceedings in the conference
“Aqua 2006”, Athens,
[8] Hopkins, D., Ducoste J., (2003), Characterising flocculation under heterogeneous turbulence. J.
Colloid Interf. Sci. 264, 184-194

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