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Temperature effects on flocculation, using different coagulants

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Temperature effects on flocculation, using different

Water Science and Technology Vol 50 No 12 pp 171–175 © IWA Publishing 2004

coagulants
C.S.B. Fitzpatrick*, E. Fradin** and J. Gregory*
* Department of Civil and Environmental Engineering, University College London, Gower St, London WC1E
6BT, UK (E-mail: c.fitzpatrick@ucl.ac.uk; j.gregory@ucl.ac.uk)
** Ecole Nationale du Genie de L’Eau et de L’Environnement de Strasbourg, 1 Quai Koch, BP 1039 F,
67070 Strasbourg Cedex, Franc (E-mail: EFRADIN@engees-e.u-strasbg.fr)

Abstract Temperature is known to affect flocculation and filter performance. Jar tests have been conducted
in the laboratory, using a photometric dispersion analyser (PDA) to assess the effects of temperature on floc
formation, breakage and reformation. Alum, ferric sulphate and three polyaluminium chloride (PACl)
coagulants have been investigated for temperatures ranging between 6 and 29°C for a suspension of kaolin
clay in London tap water. Results confirm that floc formation is slower at lower temperatures for all
coagulants. A commercial PACl product, PAX XL 19, produces the largest flocs for all temperatures; and
alum the smallest. Increasing the shear rate results in floc breakage in all cases and the flocs never reform to
their original size. This effect is most notable for temperatures around 15°C. Breakage, in terms of floc size
reduction, is greater for higher temperatures, suggesting a weaker floc. Recovery after increased shear is
greater at lower temperatures implying that floc break-up is more reversible for lower temperatures.
Keywords Coagulants; flocculation; floc breakage; floc strength; temperature effects

Introduction
Flocculation and filter performance are known to be affected by water temperature.
Temperature affects the water viscosity and the chemistry and rate of the coagulation
process.
Several researchers (e.g. Hanson and Cleasby, 1990) have reported that at lower temper-
atures flocculation is slower and flocs are smaller than at higher temperatures. Exall and
Vanloon (2000) reported that low temperatures inhibited removal of organic matter by alu-
minium sulphate (alum) and that alum is a poor cold water coagulant with or without organ-
ic matter present. In direct filtration, the slower rate of flocculation could mean that there
has been inadequate time for flocculation prior to filtration during the winter. Hanson and
Cleasby (1990) also reported that alum flocs at low temperatures were very vulnerable to
break up due to fluid shear, and that even the weakest ferric floc was stronger than the
strongest alum floc. This has implications for both flocculation and filtration. Alum is gen-
erally seen to be less effective at low temperatures, which has been attributed to lower den-
sity flocs (Hanson and Cleasby, 1990) and aggregate size (Morris and Knocke, 1984).
Recent experiments to assess the effect of flow changes on filter performance displayed
different effects for different water temperatures that could not be explained by viscosity
changes alone (Thurston et al., 2002), In general the laboratory filter displayed less parti-
cle/floc shedding in response to a flow change at lower temperatures. Preliminary jar tests
comparing alum and PAX XL1 at different temperatures showed alum flocs to be more
resistant to break-up and to recover more easily at lower temperatures.
Conventional jar tests are useful for examining floc formation and settling rates but they
do not quantify strength and re-attachment ability of the flocs. Yeung and Pelton (1996)
developed techniques to pull apart individual flocs and in doing so, contradicted earlier
theories that in fact there is no scaling relationship between floc strength and floc size. This 171
 has important implications when considering water temperature variations, as larger flocs
tend to form in warmer water, and they may not necessarily be stronger. The same research
group later added to this by suggesting that floc strength depends on the shear rate in which
flocs were formed and that conditions for optimum flocculation did not coincide with those
for maximum shear strength of flocs (Yeung et al., 1997). Similarly, Dyer and Manning
(1999) found that small flocs were, on average, of higher density than large ones and were
stronger because there are more points of contact between the particles when densely
C.S.B. Fitzpatrick et al.

packed.
The photometric dispersion analyser (PDA) was developed by Gregory and Nelson
(1986) and can be used to give an indication of floc size, breakage and reformation. This
was studied for alum flocs (Yukselen and Gregory, 2002) and it was found that breakage
occurs rapidly after an increase in shear and that alum flocs do not reform to their original
size when shear is subsequently reduced.
In this paper the effect of water temperature on floc size, strength and recovery after
shear has been examined with the aid of the PDA.

Experimental programme
All experiments were conducted using a suspension of 50 mg/l of kaolin clay in London tap
water. London tap water has a high total hardness (~280 mg/l as Ca CO3) and alkalinity
(~240 mg/l as CaCO3). The coagulants used in his study were aluminium sulphate, ferric
sulphate and 3 polyaluminium chloride products, kindly supplied by Kemira Kemi AB,
Helsingborg, Sweden. The PACl products are detailed in Table 1.
Jar tests were performed to find the optimum dose of aluminium sulphate (alum). From
these jar tests it was decided to investigate alum doses giving 3.4 mg/l Al and 1.4 mg/l Al.
Doses for the PAX coagulants were calculated to give the same concentrations of alumini-
um. Doses for ferric sulphate were chosen to give the same molar concentration of iron as
for aluminium.

Floc breakage and recovery experiments

800 ml of the kaolin suspension were put in a jar test beaker and slow stirring (50 rpm,
G = 23 s–1) was started. After 60 s the coagulant was added followed by 10 s of rapid mix at
400 rpm (G = 520 s–1). Slow stirring then continued for 600 s when the stirring rate was
increased to 400 rpm for 10 s. The stir rate was then reduced to 50 rpm again. Throughout
the formation, breakage and recovery of flocs the water was sampled at 19 ml/min. and
passed through the photometric dispersion analyser (PDA) so that the flocculation index
could be recorded. This procedure is described in a companion paper (Gregory, 2004). The
flocculation index (FI) is from the ratio of amplified RMS/DC values that are the output
from the PDA. It gives an indication of floc size.
Temperatures ranging from 6°C to 29°C were investigated. Cold water temperatures
were achieved by storing water in a refrigerator before use. Intermediate temperatures were
achieved by mixing refrigerated and tap water. The highest temperatures were achieved by
using water that had reached summer room temperatures in the laboratory. The temperature
was maintained during the lowest temperature experiments by placing the jar test beaker in

Table 1 Details of the PACl products used in this study

Product wt % Al Density (g/cm3) OH/Al ratio

PAX-XL 19 12.9 1.33 2.52

PAX-XL 1 5.2 1.24 1.95
PAX 16 8.1 1.34 1.15
172
an insulated vessel filled with iced water. In this way temperatures were controlled to
+/–1°C during an experiment.

Results and discussion

Figures 1 and 2 show the flocculation index for a range of temperatures for alum and PAX
XL19, dosing the coagulants at 1.4 mg/l Al and 3.4 mg/l Al, respectively.
It can be seen that at all temperatures PAX XL19 produces bigger flocs than alum, as

C.S.B. Fitzpatrick et al.

indicated by the flocculation index, which is related to floc size (see Gregory, 2004). The
smallest PAX flocs are bigger than the biggest alum flocs. Floc breakage occurs at 600 s
and in all cases the floc size reduced immediately. As the shear is reduced again, after 10 s,
re-growth begins but none of the flocs reach their previous size (i.e. before breakage).
For higher doses of aluminium (3.4 mg/l Al, as in Figure 2) it can be seen that floccula-
tion is much more rapid for all temperatures and that PAX XL19 shows less variation in floc
size with temperature than for the lower Al dose.
0.6
28°C pax-xl19
20°C pax-xl19
15°C pax-xl19
0.5
10°C pax-xl19
6.5°C pax-xl19
7°C alum
0.4 10.5°C alum
15°C alum
Floculation Index

20°C alum
25°C alum
0.3

Pax XL 19
0.2

0.1
Alum

0
0 200 400 600 800 1000 1200
Time (s)

Figure 1 Formation, breakage and recovery of flocs in a kaolin suspension flocculated with Alum and PAX
XL19 (dosed at 1.4 mg/l Al) at different temperatures

0.7

0.6

0.5
Floculation Index

0.4 Alum
XL19 27C
28oC XL19 15C
0.3 XL19 7C
20oC

0.2
PAX XL19
14'C o
10 C
28oC
0.1 Alum
6oC
6oC

0
0 200 400 600 800 1000 1200
Time (s)

Figure 2 Formation, breakage and recovery of flocs in a kaolin suspension flocculated with Alum and PAX
XL19 (dosed at 3.4 mg/l Al) at different temperatures. (Data for additional temperatures has been omitted
from the graph for clarity of presentation. The same trends were seen.) 173
 The average flocculation index for the first plateau just before floc break-up, due to
increased shear (FI1) was calculated for each temperature and five coagulants, dosed at the
equivalent of 1.4 mg/l Al. These results are shown in Figure 3. All of the aluminium based
coagulants show an increase in floc size with water temperature. PAX XL19 produces the
largest flocs for all temperatures, followed by PAX XL1 and then PAX 16. Alum and ferric
sulphate flocs are of a similar size, although the ferric sulphate flocs show less variation in
size with temperature. Alum produces the smallest flocs at low (winter) temperatures
C.S.B. Fitzpatrick et al.

which will have an impact on sedimentation. For similar sized flocs all year round then
ferric sulphate would seem to be the best choice. These results are consistent with those of
previous researchers.
The flocculation index data (e.g. displayed in Figure 1) can be used to obtain a floc
strength factor and a floc recovery factor (adapted from Francois, 1987). These are calcu-
lated as follows:

Strength Factor (%) = FI2/FI1 × 100

Recovery Factor (%) = (FI3–FI2)/(FI1 – FI2) × 100

0.6

0.5

0.4
Initial plateau FI value

PAX XL 19
PAX XL 1
0.3 PAX 16
Alum
ferric sulphate

0.2

0.1

0
0 5 10 15 20 25 30 35
Temperature (degrees C)

Figure 3 Variation of floc size, as indicated by flocculation index (FI), with temperature for different coagu-
lants in a kaolin suspension

50

45

40

35 Alum 1.4mg/l Al
recovery Alum 3.4 mg/l Al
30 PAX XL19 1.4 mg/l
Factor value

PAX XL1 1.4 mg/l

PAX 16 1.4mg/l
25
Linear (Alum 3.4 mg/l Al)
Linear (Alum 1.4mg/l Al)
20 Linear (PAX XL19 1.4 mg/l)
Linear (PAX XL1 1.4 mg/l)
15 Linear (PAX 16 1.4mg/l)
strength
10

0
0 5 10 15 20 25 30 35
Temperature (degrees C)

174 Figure 4 Strength and recovery factors for different coagulants, doses and temperatures
where FI1 is defined above, FI2 is the flocculation index after breakage and FI3 is the floc-
culation index after recovery to the new plateau value.
The strength and recovery factors are shown in Figure 4 for all the aluminium coagulants
used. Three important general trends are apparent:
1. Floc breakage increases with increasing temperature
2. Floc recovery/re-formation decreases with increasing temperature
3. The smaller the flocs, the less they break and the better their recovery

C.S.B. Fitzpatrick et al.

There appears to be a drop in floc re-formation ability at around 15°C, which improves a
little at temperatures above this. Further work is required to establish whether this is
significant.
Water viscosity increases as temperature decreases and this cannot explain the observed
effects. The influence of temperature on floc growth, breakage and recovery is most likely
related to changes in coagulant chemistry. It is known that hydrolysis constants for alu-
minium species change appreciably over the temperature range studied (Hanson and
Cleasby, 1990). Kinetic factors may also play a role.

Conclusions
Water temperature affects flocculation, by affecting floc size, strength and ability to re-
form after shear break-up. This will affect clarification and filtration processes, coupled
with the effects of viscosity changes due to temperature.
Warmer temperatures generally produce bigger flocs that break more easily and re-form
less well than at lower temperatures.
Aluminium based coagulants produce flocs that vary more with temperature, in size and
strength, than ferric sulphate flocs.
The PDA is an extremely useful tool for examining the relative behaviour of flocs for
changes in the flocculation conditions.

References
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and their fractal dimensions. J. Sea Research, 41, 87–95.
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175
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