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Article history: A combined electrocoagulation (EC) and electroflotation (EF) process was proposed to remove fluoride
Received 24 October 2007 from drinking water. Its efficacy was investigated under different conditions. Experimental results showed
Received in revised form 14 February 2008 that the combined process could remove fluoride effectively. The total hydraulic retention time required
Accepted 14 February 2008
was only 30 min. After treatment, the fluoride concentration was reduced from initial 4.0–6.0 mg/L to
Available online 19 February 2008
lower than 1.0 mg/L. The influent pH value was found to be a very important variable that affected fluoride
removal significantly. The optimal influent pH range is 6.0–7.0 at which not only can effective defluori-
Keywords:
dation be achieved, but also no pH readjustment is needed after treatment. In addition, it was found that
Defluoridation
Drinking water
SO4 2− had negative effect; Ca2+ had positive effect; while Cl− had little effect on the fluoride removal.
Electrocoagulation The EC charge loading, EF charge loading and energy consumption were 3.0 Faradays/m3 , 1.5 Faradays/m3 ,
Electroflotation and 1.2 kWh/m3 , respectively, under typical conditions where fluoride was reduced from initial 4.0 to
0.87 mg/L.
© 2008 Elsevier B.V. All rights reserved.
1. Introduction dialysis [11], reverse osmosis [12], and nanofiltration [13]. These
membrane processes are known to be effective means for defluori-
Fluoride has beneficial and detrimental effects on human body. dation. However, a common problem is their poor selectivity. This
It can help prevent dental cavities. However, long-term consump- not only removes the beneficial contents present in water during
tion of water containing excessive amounts of fluoride can lead defluoridation, but also increases the operational cost. Therefore,
to dental fluorosis and even to skeletal damage. According to the membrane processes are only suitable for treatment of brackish
World Health Organization (WHO) guidelines for drinking water water containing high content of fluoride, which needs both deflu-
quality, the fluoride concentration should be ≤1.5 mg/L. Unfortu- oridation and desalination simultaneously.
nately, many countries in the world are suffering from the problem In recent years, there is growing interest in EC. This technique
that the fluoride concentration in some groundwater is much can be used to treat restaurant wastewater [14], textile wastew-
higher than the guidelines value. Such groundwater should be ater [15], electroplating wastewater [16], and fluoride-containing
defluorinated when used as drinking water. In China, the upper wastewater [17,18] effectively. It has also proven its good efficacy
limit of fluoride concentration in drinking water is only 1.0 mg/L. for drinking water defluoridation [19,20]. EC is attractive in that no
Therefore, more effective defluorination techniques should be used. contaminants are introduced and beneficial contents present in raw
Nowadays, the most popular processes for drinking water deflu- water can be remained during defluoridation. The main reactions
oridation are the adsorption using activated alumina [1–3], bone involved are as following:
char [4,5], activated carbon [6,7] and other adsorbents [8,9], and
Al → Al3+ + 3e at the anode (1)
the coagulation using aluminum salts [10]. Adsorption is effec-
tive in defluoridation, but its operation is complex. Coagulation is Al3+ + 3H2 O → Al(OH)3 + 3H+ (2)
simple in equipment and effective in defluoridation under proper
Al(OH)3 + xF− → Al(OH)3−x Fx + xOH− (3)
conditions, but large amounts of contaminants such as SO4 2− are
introduced to the water, especially when the fluoride concentration 2H2 O + 2e → H2 + 2OH− at the cathode (4)
is high. Other major processes for defluoridation include electro-
Defluoridation is achieved by forming Al(OH)3−x Fx . The fine
hydrogen gas bubbles generated at the cathode can enhance F−
mass transfer and float the Al(OH)3−x Fx flocs to the top of the
∗ Corresponding author. Tel.: +86 571 87951239; fax: +86 571 87952771. EC unit. Since fluoride in the water is transferred to Al(OH)3−x Fx ,
E-mail address: chenxm@zju.edu.cn (X. Chen). Al(OH)3−x Fx must be separated effectively from the water in order
0304-3894/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2008.02.039
Q. Zuo et al. / Journal of Hazardous Materials 159 (2008) 452–457 453
Fig. 3. Change of pH after treatment (initial F− = 4.0 mg/L, EC charge load- Fig. 4. Effects of charge loading and initial fluoride concentration on defluoridation
ing = 3.0 Faradays/m3 , EF charge loading = 1.5 Faradays/m3 , hydraulic retention (influent pH 7.0, hydraulic retention time = 30 min).
time = 30 min).
3.3. Effect of coexisting ions mAl3+ + nCa2+ + (3m + 2n) H2 O = Alm Can (OH)3m+2n
affect the fluoride removal significantly, the HRT effect was inves- Table 1
Residual Al in effluent (initial F− = 4.0 mg/L, influent pH 7.0, EC charge load-
tigated at a constant charge loading by varying the applied current
ing = 3.0 Faradays/m3 , EF charge loading = 1.5 Faradays/m3 , hydraulic retention
in proportion to the water flowrate. The result is shown in Fig. 6. time = 30 min)
It was found that there was small effect of HRT on defluoridation.
Samples Residual Al in effluent (mg/L)
When HRT was 20 min, the fluoride concentration in the effluent
was 1.02 mg/L. When HRT increased to 30 min, the fluoride concen- 1# 0.83
tration decreased to 0.87 mg/L. Beyond 30 min, the effect of HRT on 2# 1.10
3# 0.90
fluoride removal was insignificant. Therefore, the optimal HRT was
about 30 min.
The slight decrease in fluoride removal efficiency at short HRT
was mainly attributed to the relatively low mass transfer rate. seen that the residual Al in the effluent ranges from 0.83 to 1.1 mg/L,
Essentially, the formation of Al(OH)3−x Fx flocs involved a series of higher than the permit value, 0.2 mg/L, of Chinese Standards for
steps, including the direct complex of Al3+ with F− during the initial Drinking Water Quality. In industrial application, therefore, EC–EF
period of time, hydrolysis of the aluminum species, mass transfer should be followed by filtration, which can remove the residual Al
of F− from the bulk solution to the Al(OH)3 flocs, and ion exchange. effectively.
Usually, most steps could be completed quickly. However, due to
the limited number of the Al(OH)3 flocs, the mass transfer of F− 4. Conclusions
from the bulk solution to the Al(OH)3 flocs was relatively low. This
caused a decrease in fluoride removal at short HRT. In addition, The combined EC and EF process could remove fluoride from
short HRT was not beneficial to flocs separation either. In the EF drinking water effectively. The total hydraulic retention time
unit, water flowed downward, while the Al(OH)3−x Fx flocs attached required was only 30 min. After treatment, the fluoride concentra-
by tiny hydrogen and oxygen bubbles moved upward. Obviously, tion was reduced from initial 4.0–6.0 mg/L to lower than 1 mg/L. It
only when the upward velocity of a floc exceeded the downward was found that the influent pH value could affect fluoride removal
velocity of the water flowrate, could the floc be separated from the significantly. The optimal influent pH is 6.0–7.0. In this influent
water. When HRT was short, the velocity of some small flocs was pH range, not only can effective defluoridation be achieved, but
lower than that of the water flow. As a result, these flocs moved out also no pH readjustment is needed after treatment. In addition,
together with the water flow, and the effluent fluoride concentra- it was found that SO4 2− had negative effect; Ca2+ had positive
tion increased. effect; while Cl− had little effect on the fluoride removal. The EC
charge loading, EF charge loading and energy consumption were
3.5. Energy consumption about 3.0 Faradays/m3 , 1.5 Faradays/m3 , and 1.2 kWh/m3 , respec-
tively, under typical conditions where fluoride was reduced from
The energy consumption of the combined EC and EF process can initial 4.0 to 0.87 mg/L at a conductivity of about 200 s/cm, a CE
be calculated according to Eq. (11): current density of 22 A/m2 , and an average EF current density of
75 A/m2 .
(n − 1)UEC I + UEF I
E= (11)
1, 000Q
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