Separation and Purification Technology 63 (2008) 642–647

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Coagulation characteristics of polyaluminum chlorides PAC-Al30

on humic acid removal from water
Panyue Zhang a,b,∗ , Zhen Wu b , Guangming Zhang c , Guangming Zeng b ,
Haiyan Zhang b , Juan Li b , Xiangguo Song b , Jinhua Dong b
a
School of Environmental Science and Engineering, Beijing Forestry University, Beijing 100083, China
b
College of Environmental Science and Engineering, Hunan University, Changsha 410082, China
c
School of Municipal & Environmental Engineering, Harbin Institute of Technology, Harbin 150090, China

a r t i c l e i n f o a b s t r a c t

Article history: Coagulants polyaluminum chlorides with a high Al30 content (PAC-Al30 ) were prepared in laboratory, and
Received 15 April 2008 the aluminum hydrolysis ratios (B = [OH− ]/[Al3+ ]) of PAC-Al30 were 1.2, 1.8 and 2.4 respectively. Coagulation
Received in revised form 26 June 2008 behaviors of PAC-Al30 with different B values and conventional coagulant AlCl3 were compared by jar test
Accepted 9 July 2008
to remove humic acid (HA) from water. Floc growth, charge neutralization capacity, HA removal and
residual aluminum concentration in the purified water were investigated. The influences of initial pH and
Keywords:
coagulant dosage on coagulation behaviors were considered. The results show that coagulants PAC-Al30
Aluminum hydrolysis ratio
exhibit much stronger floc formation capacity, have broader effective dosage range and initial pH range,
Humic acid
Residual aluminum
reach higher HA removal efficiency, and get lower residual aluminum concentration than AlCl3 does. The
Floc size coagulation/flocculation capacity of PAC-Al30 increases with the B value. The HA removal reaches 98.5% at
Zeta potential an initial pH of 7.0 and PAC-Al30 (B = 2.4) dosage of 0.16 mmol L−1 (total aluminum concentration, Alt ) when
the initial HA concentration is 10 mg L−1 ; the residual aluminum in the purified water is 0.066 mg L−1 . Al30
is verified as highly efficient coagulation/flocculation species for HA removal.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction and highest charged polycation ever characterized in PAC. Allouche

Polyaluminum chlorides (PAC) are a group of highly effective
coagulants in water treatment that have replaced a large part of
traditional aluminous coagulants in recent years because of low
dosage, high efficiency, low cost and convenient usage. In order
to improve the coagulation efficiency and to suit different condi-
tions, many sorts of PAC with different aluminum hydrolysis ratio
(B = [OH− ]/[Al3+ ]) have been produced and used, and introduction
of different ions, such as SO4 2− , SiO3 2− , Fe3+ , and organic poly-
mers into PAC has also been investigated [1]. It is generally believed
that [AlO4 Al12 (OH)24 (H2 O)12 ]7+ (Al13 ) is the most effective coagu-
lation species in polyaluminum coagulants due to its strong charge
neutralization capability, high structure stability and nanometer
molecular diameter [2,3]. But this opinion has been challenged by
the discovery of [(AlO4 )2 Al28 (OH)56 (H2 O)26 ]18+ (Al30 ), the biggest
∗ Corresponding author at: School of Environmental Science and Engineering,
Beijing Forestry University, Beijing 100083, China. Tel.: +86 731 8821228;
fax: +86 731 8822829.
E-mail addresses: zhangpy@hnu.cn, panyuez@hotmail.com (P. Zhang),
wu9 9@163.com (Z. Wu), gmgwen@gmail.com (G. Zhang), zgming@hnu.cn
(G. Zeng), zhanhaiyan9634@163.com (H. Zhang), lemonautumn@163.com (J. Li),
xiangguo637@163.com (X. Song), far44@163.com (J. Dong).
et al. [4] and Rowsell and Nazar [5] characterized the species of
Al30 by in-situ 27 Al NMR measurement, and found that Al30 is com-
posed of two ␦-Al13 connected by four aluminum monomers with a
molecule dimension of about 2.0 nm in length. With these excellent
characters, it may be a better species than Al13 .
Chen et al. [6,7] testified that Al30 species can become the dom-
inant species in polyaluminum solution when the freshly prepared
polyaluminum solution is heated at 95 ◦ C for 12 h, and the for-
mation of Al30 is accelerated by the increase of total aluminum
concentration. Allouche et al. [8] demonstrated that aluminum
monomers are the species controlling the conversion of Al13 Keg-
gin ε into Al30 . Phillips et al. [9] researched the rates of oxygen
exchange between the Al30 molecule and aqueous solution. Chen
et al. [10] found that PAC with a content of 76.8% of Al30 removes
turbidity more efficiently, and has much broader effective dosage
range and pH range when compared with high Al13 content PAC
and AlCl3 .
However, there are few reports about the Al30 coagula-
tion/flocculation performances for organic matters. In the present
research we investigated the coagulation behaviors of PAC with
a high Al30 content (PAC-Al30 ) to remove humic acids (HA), a
group of typical organics found in source water. B value is a key
parameter for PAC, which may significantly influence the hydrolytic

1383-5866/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2008.07.008
 P. Zhang et al. / Separation and Purification Technology 63 (2008) 642–647
aluminum species distribution in solution, and further affects the
coagulation/flocculation performances, the effluent quality, and
the water treatment cost. The influences of B value on the coag-
ulation/flocculation performances of PAC-Al30 were also studied.
Meanwhile, the residual aluminum concentration in the purified
water was tested.
2. Materials and methods
2.1. Coagulants and water samples
All reagents used in the research are of analytical grade. All
solutions were prepared by deionized water except for those
pointed out specifically. PAC with a high Al13 content (PAC-Al13 )
were prepared by slowly neutralizing AlCl3 solution (1.0 mol L−1 )
with NaOH solution (0.6 mol L−1 ) at room temperature under
vigorous stirring until the B value reached 1.2, 1.8 and 2.4
respectively. PAC-Al30 were prepared by heating PAC-Al13 solu-
tions with different B value at 95 ◦ C for 12 h under stirring and
refluxing. The final total aluminum concentration (Alt ) of these
PAC-Al30 and AlCl3 solutions was 0.2 mol L−1 and all solutions were
aged at room temperature for 5 days before coagulation experi-
ments.
A stock HA solution was prepared by dissolving a measured
amount of commercial HA powder in 0.1 mol L−1 NaOH solution
by high shear mixing for several hours until the HA powder dis-
solved completely. The stock HA solution was alkaline with a
HA concentration of 1 g L−1 . The working HA solution was pre-
pared by diluting a calculated amount of stock solution with tap
water and the concentration of HA was 10 mg L−1 . The alkalin-
ity concentration of the working HA solutions was adjusted to
10 mg L−1 with a NaHCO3 solution (10 g L−1 ). The pH of the work-
ing HA solutions was adjusted to a certain value with 0.1 mol L−1
HCl solution or 0.1 mol L−1 NaOH solution before coagulant addi-
tion.
2.2. Experimental and analytical methods
Coagulation experiments were carried out at room tempera-
ture using jar test on a six-paddle gang stirrer (MY3000-6B, Meiyu
Co., China). The 500 mL working HA solution was added into the
1000 mL beaker. A measured amount of coagulant was added into
the working HA solution under rapid stirring. The HA solution was
stirred rapidly at 200 rpm for 2 min after coagulant dosing, fol-
lowed by slow stirring at 30 rpm for 20 min, and then settled for
30 min.
The development of floc size during the coagulation period
was measured on a Laser Particle Size and Shape Analyzer (CIS
100, Ankersmid Co., Netherlands). After the coagulant addition
and rapid mixing, the sample was taken into the detector using
a syringe immediately. The sample in the detector was slowly
stirred under magnetic force, and the mean diameter and distri-
bution of flocs were measured once every 1 or 2 min until the floc
growth reached equilibrium. The sample was taken using a syringe
immediately after coagulant addition and rapid mixing to measure
the Zeta potential in a Zetasizer Nano ZS (3000HS, Malvern Co.,
U.K.). Supernatant sample was withdrawn and filtered through the
common qualitative filter paper for UV254 and residual aluminum
concentration measurement. UV254 representing HA concentration
was measured at 254 nm through a 2550 UV spectrophotometer
(Shimadzu Co., Japan) and residual aluminum concentration by
spectrophotometry with chrome azurol S at 620 nm through a 721
Vis spectrophotometer (Jingke Co., China) according to Standard
Examination Methods for Drinking Water–Metal Parameters (GB/T
5750.6-2006) [11].
643
3. Results and discussion
The mechanisms to explain the coagulation of humic substances
include charge neutralization, precipitation, bridge-aggregation,
adsorption and sweep-flocculation [12,13]. Under different con-
ditions, the different mechanism or their combination may be
dominant. Because of the high positive charge and big molecular
of Al30 , charge neutralization and bridge-aggregation may play a
more important role.
3.1. Study of floc development
The development of floc mean size during coagulation is shown
in Fig. 1. The order of aggregation and floc formation capacity is:
PAC-Al30 (B = 2.4) > PAC-Al30 (B = 1.8) > PAC-Al30 (B = 1.2) > AlCl3 . The
floc formation with AlCl3 begins at the 10th minute of the floccula-
tion, becomes obvious at the 20th minute, and after 36 min reaches
equilibrium with a mean floc diameter of about 175 ␮m. Coagulants
PAC-Al30 exhibit stronger floc formation capacity than AlCl3 does;
and the higher the B value is, the stronger the aggregation and floc
formation capacity are. The floc mean diameter increases rapidly
from the 4th minute after PCA-Al30 (B = 2.4) dosing and keeps stable
at 200 ␮m after 12 min flocculation. For PAC-Al30 (B = 1.8) and PAC-
Al30 (B = 1.2) the floc mean diameter begins rapid increase at the 7th
minute and the 8th minute, and the stable floc mean diameter is
194 ␮m after 16 min and 190 ␮m after 20 min flocculation respec-
tively. The particle aggregation rate depends on several factors, such
as primary particle concentration, collision efficiency, and mode
of particle transport [14]. Wang et al. [15] reported that the rapid
increase in floc size is caused by efficient collision through strong
charge neutralization, formation of a large amount of amorphous
hydroxide precipitation, the surface interaction between particles,
and the hydroxide precipitation with high specific surfaces. PAC-
Al30 are pre-hydrolyzed products of AlCl3 and possess strong charge
neutralization capability, high structure stability and nanometer
molecular diameter. All these benefit the destabilized HA particles
to adsorb to the coagulant’s surfaces to form larger flocs. Morphol-
ogy study of polyaluminum chloride and polyaluminum silicate
chloride (PASC) by transmission electron microscope also exhibited
that aluminum species aggregates (aggregation and ramification
degree) distribute in a broader size range when B value increases,
which results from the dynamic equilibrium between the aggrega-
tion and fragmentation [16]. Therefore, the increase of B value may
improve the floc development.
The floc size distribution after flocculation with different
coagulants was shown in Fig. 2. Colloids of 98% in the HA solu-
tion are smaller than 12.5 ␮m, and the floc diameter distinctly
increases after flocculation and the floc mean diameter reaches
176.25, 189.66, 194.24 and 199.13 ␮m after 42, 28, 28 and 28 min
Fig. 1. Mean floc diameter versus flocculation time after the addition of different
coagulants (dosage 0.02 mmol L−1 as Alt , initial pH 7.0).
644 P. Zhang et al. / Separation and Purification Technology 63 (2008) 642–647

Fig. 2. Floc size distribution before and after flocculation with different coagulants (dosage 0.02 mmol L−1 as Alt , initial pH 7.0).

flocculation with AlCl3 , PAC-Al30 (B = 1.2), PAC-Al30 (B = 1.8) and
PAC-Al30 (B = 2.4) respectively. For AlCl3 there is no floc larger than
310 ␮m; while the largest floc with all PAC-Al30 is over 450 ␮m,
and this trend becomes more obvious with the increase of B value.
3.2. Study of Zeta potential
Zeta potential is one of the traditional parameters that describe
the destabilization degree of colloids in water treatment. The Zeta
potential of colloids changing along with the coagulant dosage is
shown in Fig. 3. The Zeta potential ascends rapidly from negative
to positive with the coagulant dosage increase; the equipotential
dosage of PAC-Al30 (B = 2.4), PAC-Al30 (B = 1.8), PAC-Al30 (B = 1.2)
and AlCl3 is about 0.10, 0.08, 0.10 and 0.12 mmol L−1 respectively.
When the coagulant dosage is higher than 0.32 mmol L−1 , the Zeta
potential approaches a plateau with a relative high positive value
of 20–30 mV. AlCl3 exhibits lower charge neutralization capacity
than PAC-Al30 at a coagulant dosage lower than 0.32 mmol L−1 .
But the Zeta potential does not show significant difference among
PAC-Al30 with different B values, which may result from the exis-
tence of positively charged ions such as Ca2+ and Mg2+ in the HA
solution. Zhang [17] discovered that the particle Zeta potential
change becomes much more obvious when the coagulants were
added into a suspension synthesized by deionized water than by
a tap water with high hardness. When the dosage is higher than
0.32 mmol L−1 , the Zeta potential with PAC-Al30 (B = 2.4) has no sig-
nificant change, while that with other coagulants slowly ascends.
The Zeta potential with AlCl3 reaches the highest value of 30.9 mV
 P. Zhang et al. / Separation and Purification Technology 63 (2008) 642–647
Fig. 3. Effect of coagulant dosage on Zeta potential of colloids (initial pH 7.0).
at the dosage of 0.80 mmol L−1 , which may result in colloid re-
stabilization.
3.3. Effect of initial pH
With the Alt dosage of 0.02 mmol L−1 , pH reduction after coag-
ulation is lower than 0.2 in all experiments. The effect of initial
pH on HA removal is shown in Fig. 4a. It can be seen that initial
pH has an important effect on the coagulation behavior. HA are
efficiently removed by all four coagulants when the initial pH is
between 4.0 and 7.0, but the residual UV254 with AlCl3 is obviously
higher than that with PAC-Al30 at an initial pH between 7.0 and
9.0. For PAC-Al30, the suitable initial pH rang is much broader com-
pared with AlCl3 ; with the increase of B value PAC-Al30 show a
stronger ability to suit the initial pH variation. The effect of the ini-
Fig. 4. Effect of initial pH on (a) the humic acid removal, (b) the residual Al concen-
tration (coagulants dosage 0.02 mmol L−1 as Alt ).
645
tial pH on HA removal is correlated with the coagulant hydrolyzates.
When pH is lower than 5, the primary hydrolyzates of AlCl3 are
some positive hydrolyzates like Al(OH)2 + , Al(OH)2 + , Al2 (OH)2 4+ ,
Al3 (OH)4 5+ , etc. [18]. These positive hydrolyzates are easy to neu-
tralize the exterior negative charges of HA and further destabilize
the colloids, and they also benefit the physical or chemical adsorp-
tion of the destabilized HA colloids, which leads to floc growth.
When the pH is between 6 and 8, there are some high polymeric
positive hydrolyzates and Al(OH)3 formed in solution [18]. The HA
colloids are easily adsorbed, net-catched and co-precipitated by
the hydrolyzates, which have low solubility and large surface area.
When pH is higher than 8, the suspension system is difficult to be
destabilized because the hydrolyzates are transformed to Al(OH)4 −
[18]. However, PAC-Al30 show stable HA removal capacity with pH
variation (4.0–8.0) because of the structure stability of Al30 in water
[10]. Furthermore, pH also affects the physical and chemical proper-
ties of HA in water. The HA are less hydrophilic and the protonation
is improved at lower pH to make HA easier to be charge-neutralized
and destabilized.
In recent years, the physiological toxicity of aluminum is recog-
nized by people [19,20], and standards of aluminum concentration
in drinking water were issued by some organizations and govern-
ments. Standards for Drinking Water Quality of China prescribe that
the aluminum concentration in drinking water must be lower than
0.2 mg L−1 [21]. As can be seen from Fig. 4b, the residual aluminum
concentration in purified water is mostly lower than 0.2 mg L−1 at
the examined initial pH range, except for PAC-Al30 (B = 1.2) and AlCl3
at the initial pH lower than 4.0 or higher than 8.0. For all coagulants
the lowest residual aluminum concentration is obtained at the ini-
tial pH of 6.0, except for PAC-Al30 (B = 2.4) at the initial pH of 7.0.
For PAC-Al30 (B = 2.4) the residual aluminum concentration at the
initial pH of 7.0 is even lower than that in the working HA solu-
tion. That is maybe because part of the aluminum species in the
working HA solution hydrolyze and participate together during the
coagulation process.
3.4. Effect of coagulant dosage
With an initial pH of 7, the final pH decreases insignificantly after
coagulation. With the highest coagulant dosage of 0.64 mmol L−1 in
the study, the pH reduction is lower than 0.3 and 0.6 for AlCl3 and
PAC-Al30 respectively. The effect of coagulant dosage on the HA
removal is shown in Fig. 5a. With a coagulant dosage lower than
0.16 mmol L−1 the HA removal with PAC-Al30 is obviously higher
than that with AlCl3 . HA removal is 8.0%, 30.2%, 47.9% and 72.1%
at a dosage of 0.01 mmol L−1 of AlCl3 , PAC-Al30 (B = 1.2), PAC-Al30
(B = 1.8) and PAC-Al30 (B = 2.4) respectively. HA can be efficiently
removed within a dosage range from 0.12 to 0.48 mmol L−1 of these
four kinds of coagulants; and the HA removal efficiency is higher
than 95.0%. When the PAC-Al30 (B = 2.4) dosage is 0.16 mmol L−1 ,
the HA removal efficiency reaches the highest (98.5%). When the
coagulant dosage increases to 0.64 mmol L−1 , the HA solutions with
PAC-Al30 (B = 1.8), PAC-Al30 (B = 1.2) and AlCl3 exhibit serious re-
stabilization, and the HA removal efficiency is only about 62.5%. As
observed from jar test, re-stabilization occurs at high dosages for all
four coagulants; floc size decreases, floc settling slows down, and
the filtrating time increases. But this phenomenon becomes more
obvious when B value decreases. This may be related with the stable
Zeta potential of the colloids with PAC-Al30 (B = 2.4) even at a high
coagulant dosage.
As can be seen from Fig. 5b, the purified water with AlCl3
shows high residual aluminum concentration at the dosage lower
than 0.02 mmol L−1 and higher than 0.32 mmol L−1 . The resid-
ual aluminum concentration at the dosage between 0.02 and
0.32 mmol L−1 remains lower than 0.1 mg L−1 for all coagulants,
646 P. Zhang et al. / Separation and Purification Technology 63 (2008) 642–647
Fig. 5. Effect of coagulant dosage on (a) the humic acid removal, (b) the residual Al
concentration (initial pH 7.0).
and the lowest residual aluminum concentration of 0.066 mg L−1
is obtained with PAC-Al30 (B = 2.4) at a dosage of 0.16 mmol L−1 .
At the low dosage the coagulant hydrolyzates cannot neutral-
ize the HA charges adequately, the suspension system maintains
stable and the aluminum species disperse in the water. At the
appropriate dosage, the final aluminum hydrolyzates settle down
or co-precipitate with the destabilized HA. At the high dosage,
part of aluminum hydrolyzates remain still in the water because
of the system is seriously restabilized. The effect of PAC-Al30
dosage on the residual aluminum concentration is insignificant.
This may results from the relatively more stable charge neu-
tralization capability of PAC-Al30 and more stable HA removal
efficiency.
3.5. Effects of other factors
The effects of calcium ions and turbidity-contributing mate-
rials in water on coagulation were also tested. With PAC-Al30
(B = 2.4) dosage (as Alt ) lower than 0.02 mmol L−1 , the presence
of calcium ions and turbidity-contributing materials improves
the HA removal. With the PAC-Al30 (B = 2.4) dosage (as Alt ) of
0.01 mmol L−1 , 2 mmol L−1 calcium ions increases HA removal
by 53.4%, and with the PAC-Al30 (B = 2.4) dosage (as Alt ) of
0.02 mmol L−1 , 50 mg L−1 kaolin increases HA removal by 32.4%.
These effects accord with the results from other researchers [12,22].
The calcium ions seem to block negatively charged groups of
the surface molecules reducing electrostatic repulsion and act as
bridges between functional groups of two adjacent molecules.
Kaolin particles adsorb the HA and then they are removed
together. When the PAC-Al30 (B = 2.4) dosage (as Alt ) exceeds
0.02 mmol L−1 , the effects of calcium ions and kaolin become
insignificant.
4. Conclusions
Compared with AlCl3 , coagulants PAC-Al30 with a high Al30
content have stronger floc formation capacity, broader efficient
pH range and wider coagulant dosage range. Al30 is a highly
efficient coagulation/flocculation species for HA removal. The coag-
ulation/flocculation capacity of PAC-Al30 is influenced by the B
value, and the higher B value, the stronger aggregation and floc for-
mation capacity of coagulant. PAC-Al30 with a B value of 2.4 exhibits
the highest UV254 removal efficiency and lower residual aluminum
concentration at a broader pH range and a wider dosage range.
The presence of calcium ions and turbidity-contributing materi-
als improves the HA removal. The HA removal reaches 98.5% at
an initial pH of 7.0 and PAC-Al30 (B = 2.4) dosage of 0.16 mmol L−1
(as Alt ) when an initial HA concentration is 10 mg L−1 ; and
the residual aluminum concentration in the purified water is
0.066 mg L−1 .
Acknowledgements
This work was supported by Program for New Century Excellent
Talents in University (NCET) and Program for Changjiang Scholars
and Innovative Research Team in University (PCSIRT).
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