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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


et al. [4] and Rowsell and Nazar [5] characterized the species of
Polyaluminum chlorides (PAC) are a group of highly effective Al30 by in-situ 27 Al NMR measurement, and found that Al30 is com-
coagulants in water treatment that have replaced a large part of posed of two ␦-Al13 connected by four aluminum monomers with a
traditional aluminous coagulants in recent years because of low molecule dimension of about 2.0 nm in length. With these excellent
dosage, high efficiency, low cost and convenient usage. In order characters, it may be a better species than Al13 .
to improve the coagulation efficiency and to suit different condi- Chen et al. [6,7] testified that Al30 species can become the dom-
tions, many sorts of PAC with different aluminum hydrolysis ratio inant species in polyaluminum solution when the freshly prepared
(B = [OH− ]/[Al3+ ]) have been produced and used, and introduction polyaluminum solution is heated at 95 ◦ C for 12 h, and the for-
of different ions, such as SO4 2− , SiO3 2− , Fe3+ , and organic poly- mation of Al30 is accelerated by the increase of total aluminum
mers into PAC has also been investigated [1]. It is generally believed concentration. Allouche et al. [8] demonstrated that aluminum
that [AlO4 Al12 (OH)24 (H2 O)12 ]7+ (Al13 ) is the most effective coagu- monomers are the species controlling the conversion of Al13 Keg-
lation species in polyaluminum coagulants due to its strong charge gin ε into Al30 . Phillips et al. [9] researched the rates of oxygen
neutralization capability, high structure stability and nanometer exchange between the Al30 molecule and aqueous solution. Chen
molecular diameter [2,3]. But this opinion has been challenged by et al. [10] found that PAC with a content of 76.8% of Al30 removes
the discovery of [(AlO4 )2 Al28 (OH)56 (H2 O)26 ]18+ (Al30 ), the biggest turbidity more efficiently, and has much broader effective dosage
range and pH range when compared with high Al13 content PAC
and AlCl3 .
∗ Corresponding author at: School of Environmental Science and Engineering, However, there are few reports about the Al30 coagula-
Beijing Forestry University, Beijing 100083, China. Tel.: +86 731 8821228; tion/flocculation performances for organic matters. In the present
fax: +86 731 8822829. research we investigated the coagulation behaviors of PAC with
E-mail addresses: zhangpy@hnu.cn, panyuez@hotmail.com (P. Zhang),
a high Al30 content (PAC-Al30 ) to remove humic acids (HA), a
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), group of typical organics found in source water. B value is a key
xiangguo637@163.com (X. Song), far44@163.com (J. Dong). 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) 642–647 643

aluminum species distribution in solution, and further affects the 3. Results and discussion
coagulation/flocculation performances, the effluent quality, and
the water treatment cost. The influences of B value on the coag- The mechanisms to explain the coagulation of humic substances
ulation/flocculation performances of PAC-Al30 were also studied. include charge neutralization, precipitation, bridge-aggregation,
Meanwhile, the residual aluminum concentration in the purified adsorption and sweep-flocculation [12,13]. Under different con-
water was tested. ditions, the different mechanism or their combination may be
dominant. Because of the high positive charge and big molecular
2. Materials and methods of Al30 , charge neutralization and bridge-aggregation may play a
more important role.
2.1. Coagulants and water samples
3.1. Study of floc development
All reagents used in the research are of analytical grade. All
solutions were prepared by deionized water except for those The development of floc mean size during coagulation is shown
pointed out specifically. PAC with a high Al13 content (PAC-Al13 ) in Fig. 1. The order of aggregation and floc formation capacity is:
were prepared by slowly neutralizing AlCl3 solution (1.0 mol L−1 ) PAC-Al30 (B = 2.4) > PAC-Al30 (B = 1.8) > PAC-Al30 (B = 1.2) > AlCl3 . The
with NaOH solution (0.6 mol L−1 ) at room temperature under floc formation with AlCl3 begins at the 10th minute of the floccula-
vigorous stirring until the B value reached 1.2, 1.8 and 2.4 tion, becomes obvious at the 20th minute, and after 36 min reaches
respectively. PAC-Al30 were prepared by heating PAC-Al13 solu- equilibrium with a mean floc diameter of about 175 ␮m. Coagulants
tions with different B value at 95 ◦ C for 12 h under stirring and PAC-Al30 exhibit stronger floc formation capacity than AlCl3 does;
refluxing. The final total aluminum concentration (Alt ) of these and the higher the B value is, the stronger the aggregation and floc
PAC-Al30 and AlCl3 solutions was 0.2 mol L−1 and all solutions were formation capacity are. The floc mean diameter increases rapidly
aged at room temperature for 5 days before coagulation experi- from the 4th minute after PCA-Al30 (B = 2.4) dosing and keeps stable
ments. at 200 ␮m after 12 min flocculation. For PAC-Al30 (B = 1.8) and PAC-
A stock HA solution was prepared by dissolving a measured Al30 (B = 1.2) the floc mean diameter begins rapid increase at the 7th
amount of commercial HA powder in 0.1 mol L−1 NaOH solution minute and the 8th minute, and the stable floc mean diameter is
by high shear mixing for several hours until the HA powder dis- 194 ␮m after 16 min and 190 ␮m after 20 min flocculation respec-
solved completely. The stock HA solution was alkaline with a tively. The particle aggregation rate depends on several factors, such
HA concentration of 1 g L−1 . The working HA solution was pre- as primary particle concentration, collision efficiency, and mode
pared by diluting a calculated amount of stock solution with tap of particle transport [14]. Wang et al. [15] reported that the rapid
water and the concentration of HA was 10 mg L−1 . The alkalin- increase in floc size is caused by efficient collision through strong
ity concentration of the working HA solutions was adjusted to charge neutralization, formation of a large amount of amorphous
10 mg L−1 with a NaHCO3 solution (10 g L−1 ). The pH of the work- hydroxide precipitation, the surface interaction between particles,
ing HA solutions was adjusted to a certain value with 0.1 mol L−1 and the hydroxide precipitation with high specific surfaces. PAC-
HCl solution or 0.1 mol L−1 NaOH solution before coagulant addi- Al30 are pre-hydrolyzed products of AlCl3 and possess strong charge
tion. neutralization capability, high structure stability and nanometer
molecular diameter. All these benefit the destabilized HA particles
2.2. Experimental and analytical methods to adsorb to the coagulant’s surfaces to form larger flocs. Morphol-
ogy study of polyaluminum chloride and polyaluminum silicate
Coagulation experiments were carried out at room tempera- chloride (PASC) by transmission electron microscope also exhibited
ture using jar test on a six-paddle gang stirrer (MY3000-6B, Meiyu that aluminum species aggregates (aggregation and ramification
Co., China). The 500 mL working HA solution was added into the degree) distribute in a broader size range when B value increases,
1000 mL beaker. A measured amount of coagulant was added into which results from the dynamic equilibrium between the aggrega-
the working HA solution under rapid stirring. The HA solution was tion and fragmentation [16]. Therefore, the increase of B value may
stirred rapidly at 200 rpm for 2 min after coagulant dosing, fol- improve the floc development.
lowed by slow stirring at 30 rpm for 20 min, and then settled for The floc size distribution after flocculation with different
30 min. coagulants was shown in Fig. 2. Colloids of 98% in the HA solu-
The development of floc size during the coagulation period tion are smaller than 12.5 ␮m, and the floc diameter distinctly
was measured on a Laser Particle Size and Shape Analyzer (CIS increases after flocculation and the floc mean diameter reaches
100, Ankersmid Co., Netherlands). After the coagulant addition 176.25, 189.66, 194.24 and 199.13 ␮m after 42, 28, 28 and 28 min
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 Fig. 1. Mean floc diameter versus flocculation time after the addition of different
5750.6-2006) [11]. 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 When the coagulant dosage is higher than 0.32 mmol L−1 , the Zeta
PAC-Al30 (B = 2.4) respectively. For AlCl3 there is no floc larger than potential approaches a plateau with a relative high positive value
310 ␮m; while the largest floc with all PAC-Al30 is over 450 ␮m, of 20–30 mV. AlCl3 exhibits lower charge neutralization capacity
and this trend becomes more obvious with the increase of B value. than PAC-Al30 at a coagulant dosage lower than 0.32 mmol L−1 .
But the Zeta potential does not show significant difference among
3.2. Study of Zeta potential 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
Zeta potential is one of the traditional parameters that describe solution. Zhang [17] discovered that the particle Zeta potential
the destabilization degree of colloids in water treatment. The Zeta change becomes much more obvious when the coagulants were
potential of colloids changing along with the coagulant dosage is added into a suspension synthesized by deionized water than by
shown in Fig. 3. The Zeta potential ascends rapidly from negative a tap water with high hardness. When the dosage is higher than
to positive with the coagulant dosage increase; the equipotential 0.32 mmol L−1 , the Zeta potential with PAC-Al30 (B = 2.4) has no sig-
dosage of PAC-Al30 (B = 2.4), PAC-Al30 (B = 1.8), PAC-Al30 (B = 1.2) nificant change, while that with other coagulants slowly ascends.
and AlCl3 is about 0.10, 0.08, 0.10 and 0.12 mmol L−1 respectively. The Zeta potential with AlCl3 reaches the highest value of 30.9 mV
P. Zhang et al. / Separation and Purification Technology 63 (2008) 642–647 645

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
Fig. 3. Effect of coagulant dosage on Zeta potential of colloids (initial pH 7.0). 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
at the dosage of 0.80 mmol L−1 , which may result in colloid re- is improved at lower pH to make HA easier to be charge-neutralized
stabilization. and destabilized.
In recent years, the physiological toxicity of aluminum is recog-
3.3. Effect of initial pH nized by people [19,20], and standards of aluminum concentration
in drinking water were issued by some organizations and govern-
With the Alt dosage of 0.02 mmol L−1 , pH reduction after coag- ments. Standards for Drinking Water Quality of China prescribe that
ulation is lower than 0.2 in all experiments. The effect of initial the aluminum concentration in drinking water must be lower than
pH on HA removal is shown in Fig. 4a. It can be seen that initial 0.2 mg L−1 [21]. As can be seen from Fig. 4b, the residual aluminum
pH has an important effect on the coagulation behavior. HA are concentration in purified water is mostly lower than 0.2 mg L−1 at
efficiently removed by all four coagulants when the initial pH is the examined initial pH range, except for PAC-Al30 (B = 1.2) and AlCl3
between 4.0 and 7.0, but the residual UV254 with AlCl3 is obviously at the initial pH lower than 4.0 or higher than 8.0. For all coagulants
higher than that with PAC-Al30 at an initial pH between 7.0 and the lowest residual aluminum concentration is obtained at the ini-
9.0. For PAC-Al30, the suitable initial pH rang is much broader com- tial pH of 6.0, except for PAC-Al30 (B = 2.4) at the initial pH of 7.0.
pared with AlCl3 ; with the increase of B value PAC-Al30 show a For PAC-Al30 (B = 2.4) the residual aluminum concentration at the
stronger ability to suit the initial pH variation. The effect of the ini- 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-
Fig. 4. Effect of initial pH on (a) the humic acid removal, (b) the residual Al concen- ual aluminum concentration at the dosage between 0.02 and
tration (coagulants dosage 0.02 mmol L−1 as Alt ). 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

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).

References

[1] P. Zhang, H.H. Hahn, E. Hoffmann, G. Zeng, Influence of some additives to alu-
minium species distribution in aluminium coagulants, Chemosphere 57 (2004)
1489–1494.
[2] N. Pasrthasarathy, J. Buffle, Study of polymeric aluminum (III) hydroxide solu-
tions for application in wastewater treatment: properties of the polymer and
Fig. 5. Effect of coagulant dosage on (a) the humic acid removal, (b) the residual Al
optimal conditions preparation, Water Res. 19 (1985) 25–36.
concentration (initial pH 7.0).
[3] C.Z. Hu, H.J. Liu, J.H. Qu, D.S. Wang, J. Ru, Coagulation behavior of aluminum
salts in eutrophic water: significance of Al13 species and pH control, Environ.
Sci. Technol. 40 (2006) 325–331.
and the lowest residual aluminum concentration of 0.066 mg L−1 [4] L. Allouche, C. Gérardin, T. Loiseau, G. Férey, F. Taulelle, Al30 : a giant aluminum
polycation, Angew. Chem. Int. Ed. 39 (2000) 511–514.
is obtained with PAC-Al30 (B = 2.4) at a dosage of 0.16 mmol L−1 . [5] J. Rowsell, L.F. Nazar, Speciation and thermal transformation in alumina sols:
At the low dosage the coagulant hydrolyzates cannot neutral- structures of the polyhydroxyoxoaluminum cluster [Al2 O8 (OH)56 (H2 O)26 ]18+
ize the HA charges adequately, the suspension system maintains and its ␦-Keggin moieté, J. Am. Chem. Soc. 122 (2000) 3777–3778.
[6] Z.Y. Chen, C.J. Liu, Z.K. Luan, Z.G. Zhang, Y.Z. Li, Z.P. Jia, Effect of total aluminium
stable and the aluminum species disperse in the water. At the concentration on the formation and transformation of nanosized Al13 and Al30
appropriate dosage, the final aluminum hydrolyzates settle down in hydrolytic polymeric aluminium aqueous solutions, Chin. Sci. Bull. 50 (2005)
or co-precipitate with the destabilized HA. At the high dosage, 2010–2015.
[7] Z.Y. Chen, Z.K. Luan, J.H. Fan, Z.G. Zhang, X.J. Peng, B. Fan, Effect of thermal
part of aluminum hydrolyzates remain still in the water because
treatment on the formation and transformation of Keggin Al13 and Al30 species
of the system is seriously restabilized. The effect of PAC-Al30 in hydrolytic aluminium solutions, Colloids Surf. A 292 (2007) 110–118.
dosage on the residual aluminum concentration is insignificant. [8] L. Allouche, F. Taulelle, Conversion of Al13 Keggin ε into Al30 : a reaction con-
trolled by aluminium monomers, Inorg. Chem. Commun. 6 (2003) 1167–1170.
This may results from the relatively more stable charge neu-
[9] B.L. Phillips, A. Lee, W.H. Casey, Rates of oxygen exchange between
tralization capability of PAC-Al30 and more stable HA removal the Al2 O8 Al28 (OH)56 (H2 O)26 18+ (aq) (Al30 ) molecule and aqueous solution,
efficiency. Geochim. Cosmochim. Acta 67 (2003) 2725–2733.
[10] Z.Y. Chen, B. Fan, X.J. Peng, Z.G. Zhang, J.H. Fan, Z.K. Luan, Evaluation of Al30
polynuclear species in polyaluminum solutions as coagulant for water treat-
3.5. Effects of other factors ment, Chemosphere 64 (2006) 912–918.
[11] Ministry of Health of the People’s Republic of China, Standardization Admin-
The effects of calcium ions and turbidity-contributing mate- istration of the People’s Republic of China, Standards examination methods
for drinking water–metal parameters (GB/T 5750.6-2006), Standards Press of
rials in water on coagulation were also tested. With PAC-Al30 China, Beijing, 2006.
(B = 2.4) dosage (as Alt ) lower than 0.02 mmol L−1 , the presence [12] W.P. Cheng, F.H. Chi, C.C. Li, R.F. Yu, A study on the removal of organic sub-
of calcium ions and turbidity-contributing materials improves stances from low-turbidity and low-alkalinity water with metal-polysilicate
coagulants, Colloids Surf. A 312 (2008) 238–244.
the HA removal. With the PAC-Al30 (B = 2.4) dosage (as Alt ) of [13] J.-M. Siéliéchi, B.S. Lartiges, G.J. Kayem, S. Hupont, C. Frochot, J. Thieme, J. Ghan-
0.01 mmol L−1 , 2 mmol L−1 calcium ions increases HA removal baja, J.B. d’Espinose de la Caillerie, O. Barrès, R. Kamga, P. Levitz, L.J. Michot,
by 53.4%, and with the PAC-Al30 (B = 2.4) dosage (as Alt ) of Changes in humic acid conformation during coagulation with ferric chloride:
implications for drinking water treatment, Water Res. 42 (2008) 2111–2123.
0.02 mmol L−1 , 50 mg L−1 kaolin increases HA removal by 32.4%.
[14] H.H. Hahn, W. Stumm, Kinetics of coagulation with hydrolyzed Al(III): the rate-
These effects accord with the results from other researchers [12,22]. determining step, J. Colloid Interface Sci. 28 (1968) 134–144.
The calcium ions seem to block negatively charged groups of [15] D.S. Wang, H.X. Tang, J. Gregory, Relative importance of charge neutralization
and precipitation on coagulation of kaolin with PACl: effect of sulphate ion,
the surface molecules reducing electrostatic repulsion and act as
Environ. Sci. Technol. 36 (2002) 1815–1820.
bridges between functional groups of two adjacent molecules. [16] B.Y. Gao, Q.Y. Yue, C.S. Wang, Transmission electron microscopic observation on
Kaolin particles adsorb the HA and then they are removed morphology of polyaluminum silicate chloride flocculant, Shanghai Environ.
together. When the PAC-Al30 (B = 2.4) dosage (as Alt ) exceeds Sci. 20 (2001) 414–422 (in Chinese).
[17] P. Zhang, Herstellung und Characterisierung Polymerer Anorganischer Flock-
0.02 mmol L−1 , the effects of calcium ions and kaolin become ungsmittel, Ph.D. Dissertation, University of Karlsruhe, Ernst Grässer, Karlsruhe,
insignificant. 2003.
P. Zhang et al. / Separation and Purification Technology 63 (2008) 642–647 647

[18] J.M. Duan, J. Gregory, Coagulation by hydrolysing metal salts, Adv. Colloid Inter- [21] Ministry of Health of the People’s Republic of China, Standardization Adminis-
face Sci. 100–102 (2003) 475–502. tration of the People’s Republic of China, Standards for drinking water quality
[19] G. Berthon, Chemical speciation studies in relation to aluminium metabolism (GB 5749-2006), Standards Press of China, Beijing, 2006.
and toxicity, Coord. Chem. Rev. 149 (1996) 241–280. [22] M. Brigante, G. Zanini, M. Avena, On the dissolution kinetics of humic acid
[20] G. Berthon, Aluminium speciation in relation to aluminium bioavailability, particles: effects of pH, temperature and Ca2+ concentration, Colloids Surf. A
metabolism and toxicity, Coord. Chem. Rev. 228 (2002) 319–341. 294 (2007) 64–70.