Separation and Purification Technology 36 (2004) 33–39

New bipolar electrocoagulation–electroflotation process

for the treatment of laundry wastewater
Jiantuan Ge, Jiuhui Qu∗ , Pengju Lei, Huijuan Liu
State Key Laboratory for Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences,
Chinese Academy of Sciences, Beijing 100085, China

Received 11 January 2003; received in revised form 9 April 2003; accepted 22 April 2003

Abstract

A new bipolar electrocoagulation and electroflotation process was developed to treat laundry wastewater. In this new process,
electrocoagulation and electroflotation were carried out simultaneously in a single reactor. The operating parameters such as
initial pH, hydraulic residence time (HRT) and current density were investigated. The unique design of the reactor made it
possible for the effective removal of turbidity, COD, phosphate and surfactant (MBAS) in a wide pH range (5–9) at a short HRT
(5–10 min). The pilot scale tests (1.5 m3 /h) were carried out successfully in three different places suggested that the bipolar
electrocoagulation–electroflotation process was feasible for the treatment of laundry wastewater.
© 2003 Elsevier B.V. All rights reserved.

Keywords: Laundry wastewater; Electrocoagulation; Electroflotation; Electrochemical reactor; Field test

1. Introduction lation, electroflotation and electrochemical oxidation,

Traditional methods for dealing with laundry
wastewater consist of various combinations of bio-
logical, physical and chemical methods [1–3]. Due to
the large variability of the composition of this kind
of wastewater, most of these traditional methods are
becoming inadequate, especially for the simultane-
ous removal of high content of suspended solids,
surfactants and phosphate. Hence a search for more
cost-effective treatment methods is in need.
A variety of very promising techniques based on
electrochemical technology, including electrocoagu-
∗ Corresponding author. Tel.: +86-10-6284-9137;
fax: +86-10-6284-9160.
E-mail address: jhqu@mail.rcees.ac.cn (J. Qu).
have been developed for the treatment of wastewater.
Amongst them, electrocoagulation has been used to
treat urban wastewater [4], oil wastes [5], dyes [6],
suspended particles [7], chemical and mechanical pol-
ishing waste [8], organic contaminants from landfill
leachates [9], defluoridation [10] and heavy metal-
containing solutions [11]. It was found that anodized
aluminum was more effective than the aluminum ion
introduced in the form of aluminum sulfate solution
[12]. However, preliminary experiment in our labo-
ratory showed that the hydrogen gas produced at the
aluminum cathode in an electrocoagulation cell was
not so fine that could float only about 60% of the total
solids.
In this study, a combinative bipolar electrocoagul-
ation–electroflotation process was developed to treat

1383-5866/$ – see front matter © 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S1383-5866(03)00150-3
34 J. Ge et al. / Separation and Purification Technology 36 (2004) 33–39
laundry wastewater. The primary objectives of using
the new reactor were to neutralize pollutant charge,
generate ultra-fine bubbles and separate the coagulated
flocs from water. Finally, pilot scale field tests (1.5
m3 /h) were carried out in three different places.
2. Description of bipolar
electrocoagulation–electroflotation
In the bipolar electrocoagulation–electroflotation
unit (Fig. 1), three aluminum plates placed between
two titanium electrodes having opposite charges will
undergo anodic reactions on the positive side while
on the negative side cathodic reactions take place.
The main anodic reactions are as follows:
Ti anode : 2H2 O → O2 + 4H+ + 4e
Al positive side : Al → Al 3+
+ 3e
The hydrolysis and polymerization of Al3+
un-
der appropriate pH conditions subsequently give
rise to the formation of such species as Al(OH)2+ ,
Al2 (OH)2 4+ , Al(OH)3 and charged hydroxo cationic
complexes [13], which can effectively remove pollu-
tants by adsorption to produce charge neutralization,
and by enmeshment in a precipitate. In this study, tita-
nium metal is chosen as anode material mainly for its
Fig. 1. Schematic representation of the bipolar electrocoagula-
tion–electroflotation.
cheapness. Excellent materials for oxygen evolution
have also been reported [14–16].
Since some amount of NaCl always exists in the
laundry wastewater, other reactions may be also en-
countered in anodic compartment:
2Cl− → Cl2 + 2e (3)
Cl2 + H2 O → HClO + H+ + Cl− (4)
HClO → H+ + ClO− (5)
While the main cathodic reaction on the Ti cathode
and negative side of aluminum is as follows:
2H2 O + 2e → H2 + 2OH− (6)
Other reactions could be observed at the cathode
surface and bring about the precipitation of the car-
bonate salt.
(1)
HCO− − 2−
3 + OH → CO3 + H2 O (7)
(2)
Ca2+ + CO2−
3 → CaCO3 (8)
Mg2+ + CO2−
3 → MgCO3 (9)
These will increase the ohmic resistance of the elec-
trochemical cell. However, alternating current direc-
tion (ACD) at due time can be applied to alleviate the
precipitation of carbonate salt on the electrode surface.
3. Experimental
The experimental setup is schematically shown in
Fig. 2. The system includes mainly a 2.8-dm3 electro-
chemical reactor and an 11.2-dm3 separator. The elec-
trochemical reactor is composed of four sets of bipolar
electrocoagulation–electroflotation unit. The Ti elec-
trodes are connected to the D.C. power only. There are
eight pieces of Ti plates and 21 pieces of Al plates.
The dimensions of the Ti electrode and Al electrode
are 100 × 60 × 2 mm and 100 × 60 × 3 mm, respec-
tively. The effective area of each electrode is 50 cm2
and the spacing between electrodes is 8 mm. The sep-
arator consists of an outer cylinder with a diameter of
100 mm and an inner tube with a diameter of 20 mm.
The wastewater collected from Huaqing Laundry
House in Tsinghua University was used for all the
experiments except for pilot-scale field tests. The
wastewater entered the electrochemical reactor from
 J. Ge et al. / Separation and Purification Technology 36 (2004) 33–39
Fig. 2. Flowchart of the experimental system: (1) DC power supply, (2) pump, (3) electrochemical cell (solid bar: Ti electrode and space
bar: Al electrode), (4) polymer electrolyte injection, (5) separator and (6) effluent.
the bottom, moved upwards in a zig-zag pattern from
the spacing between electrodes. It flowed out the re-
actor from the top. After adding desired amount of
polyelectrolytes (PAM), the coagulated wastewater
was introduced from the bottom of the inner tube
of the separator. The treated wastewater exited from
the lower part of the separator. The floated sludge
could either be removed from the top of the separa-
tor (laboratory tests) or recycled back to the influent
wastewater tank (pilot-scale field tests).
Chemical oxygen demand (COD), surfactants
(MBAS) and phosphate (P-PO4 3− ) were measured
according to the Standard Methods [17]. Turbidity
was recorded on a 2100N IS Turbidimeter (Hach).
The pH of the wastewater was adjusted with H2 SO4
and NaOH and the measurement was performed on a
720A pH Meter (Orion).
4. Results and discussion
4.1. Laboratory test of laundry wastewater
First we carried out laboratory experiments of
laundry wastewater to investigate the variables such
as hydraulic residence time (HRT), initial pH and
current density that may influence the processes of
electrocoagulation–electroflotation. The electrical
35
current direction was automatically alternated every
15 min to alleviate passivation of the electrodes.
4.1.1. pH change during the bipolar
electrocoagulation–electroflotation process
It has been established that the influent pH is of
vital importance in the performance of many elec-
trochemical process and chemical coagulation oper-
ations. To examine the effect of pH on the bipolar
electrocoagulation–electroflotation process, the laun-
dry wastewater was adjusted to the desired pH with
diluted aqueous sodium hydroxide or sulfuric acid.
The results illustrated in Fig. 3 demonstrated the
removal efficiencies of MBAS, turbidity, COD and
phosphate as a function of the influent pH. With 1
mg/l PAM alone, the removal efficiencies were negli-
gible. It was found that the optimum pH for turbidity,
MBAS, COD and phosphate was around 5–9. How-
ever, the turbidity removal dropped dramatically at
pH < 4 or >9. A slight drop in COD, phosphate and
MBAS removal was observed at pH>10. These re-
sults can be explained by the species distribution of
aluminum ions. In the pH range 5–9 the hydrolysis
and polymerization of Al3+ give rise to the formation
of such species as Al(OH)2+ , Al2 (OH)2 4+ , Al(OH)3
and charged hydroxo cationic complexes such as
Al13 (OH)32 7+ , which are efficient for coagulation
[18,19]. When pH was greater than 10, the main
36 J. Ge et al. / Separation and Purification Technology 36 (2004) 33–39
Fig. 3. Removal efficiencies of COD, MBAS, phosphate and tur-
bidity as a function of initial pH (HRT, 10 min; I, 1.2A; PAM, 1
mg/l).
hydrolysis product is Al(OH)4 − , which does not fa-
vor the formation of anodized aluminum species and
the adsorption of dispersed solids. At low pH where
one has only aluminum ion, the adsorption effect is
insignificant [20].
The removal of surfactant in this process may be
assumed that the surfactant is first adsorbed on the
particulate surface, making the surface hydrophobic,
and thus forcing the particulate to the surface of the
rising bubble. Finally the surfactant-particulate-bubble
composite is floated to the surface. The reduction of
COD may be mainly accomplished by electrocoag-
ulation, electroflotation, direct anodic oxidation and
indirect oxidation by chloride ions. Electrochemically
produced aluminum has been found to be more effi-
cient in removing phosphate than the same amount
of aluminum contained in an aluminum sulfate so-
lution [21]. In brief, the bipolar electrocoagulation–
electroflotation process includes electroflotation of
suspended pollutants, electrocoagulation of colloidal
pollutants, electrodestruction of dissolved organics
and electrodeposition of dissolved inorganics.
It was found that after electrocoagulation–electro-
flotation process, the pH of the aqueous medium
could be neutralized to some extent (Fig. 4). This phe-
nomenon can be explained according to reactions (1)–
(9) and the following chemical reactions:
Al + 3H+ → Al3+ (10)
Al3+ + 3H2 O → Al(OH)3 + 3H+ (11)
Al(OH)3 + OH− → Al(OH)−
4 (12)
Fig. 4. pH change during bipolar electrocoagulation–electro-
flotation process (HRT, 10 min; I, 1.0 A).
In acidic medium, CO2 is over saturated and re-
leased from the wastewater due to H2 and O2 bub-
ble ‘purge’, which causes a pH increase. In addition,
the chemical dissolution of Al (Reaction 10) will con-
sume H+ and gives rise to the pH increase. Moreover,
reaction (11) will shift towards the left side and again
results in an increase in pH. At high pH condition,
reactions (7)–(9) will proceed readily and reaction (12)
may take place, both lead to a pH decrease.
The pH neutralization effect made this process ef-
fective in a much wider pH range, which made it su-
perior to traditional chemical coagulation. The latter
is highly sensitive to pH change and effective coagu-
lation is achieved at pH 6–7 [22].
4.1.2. Effect of HRT in the electrochemical reactor
The influence of HRT on the process was studied
on the COD removal at the desired HRT where other
parameters were kept unchanged. Here HRT should
be defined as the ratio of the total volume of the elec-
trochemical reactor to wastewater flow rate. Fig. 5
showed that the removal of COD increased with in-
creasing HRT. But when HRT was greater than 10
min, the removal of COD reached a plateau. This is
a very attractive feature for densely populated areas
where the compactness of the treatment facility is
particularly concerned. The mechanism of the elec-
trochemical process in aqueous system is quite com-
plex [23]. It is generally believed that there are three
possible mechanisms involved in the process: elec-
trocoagulation, electroflotation and electrooxidation.
However, it can be suggested that, during the bipolar
 J. Ge et al. / Separation and Purification Technology 36 (2004) 33–39
Fig. 5. COD removal efficiencies as a function of HRT (I, 1.0 A).
electrocoagulation–electroflotation process, bipolar
aluminum electrodes are mainly responsible for elec-
trocoagulation. A relatively large amount of fine H2
and O2 gas evolution from Ti electrodes satisfies the
needs for electroflotation to float the flocs formed by
electrocoagulation and other pollutants to the surface.
The conditions present in the electrocoagulation–
electroflotation cell favored formation of the micro-
bubble-pollutant aggregate composite after the
collision and union of the two occurred in the sub-
sequent separation unit. On the whole, the configu-
ration of the reactor can be considered as plug flow.
But the plug flow reactor (PFR) was comprised of
many micro continuous stirred tank reactors (CSTR)
present in two electrodes. Typical bubble sizes in
electroflotation always fall in the range of 20–70 ␮m
[24], smaller than those by electrocoagulation or con-
ventional flotation, providing both sufficient sites for
gas–liquid–solid interface and mixing effect to ac-
complish aggregation of tiny destabilized particulates.
The PFR made it possible for the high removal of
pollutants at a short HRT. Basically, the capture of the
micro-bubble by the pollutant was rather irreversible
under the operating conditions of an electrocoagula-
tion cell. This fundamental mechanism distinguished
the electrocoagulation–electroflotation process from
the combination of electrocoagulation and dissolved
aeration flotation (DAF).
4.1.3. Effect of electrical current
Fig. 6 showed the removal of turbidity, COD and
MBAS as a function of electric current. It was found
37
Fig. 6. Removal of turbidity, COD and MBAS as a function of
current density (HRT, 5 min).
that the removal of turbidity, COD and MBAS was
increased with increasing current. The influence of
current density should be correlated with HRT in the
continuous operating system. According to Faraday’s
law, the amount of aluminum dissolved electrochem-
ically is proportional to charge loadings. When 1 F
(26.8 Ah) passes through the electric circuit, 0.0224
Nm3 hydrogen gas will be evolved, which is much
greater than the volume of gas released in traditional
DAF. Consequently, increasing current density will
give rise to an increase in charge loading and leading
to increased removal of pollutants [25]. Furthermore,
better collection efficiencies could be reached during
electroflotation by obtaining smaller bubbles with
increasing current density [26].
4.2. Pilot-scale field tests (1.5 m3 /h)
Based on the laboratory test of laundry wastew-
ater, 1.5 m3 /h electrocoagulation–electroflotation
equipment was manufactured and mounted on a mo-
bile truck. The equipment mainly consisted of an
electrocoagulation–electroflotation tank and a sep-
arator. The corresponding dimensions of are D450
× 1600 mm and D400 × 1600 mm, respectively.
The electrode gap was 20 mm. The floated sludge
flowed out from the separator and was discharged
into the feed tank, which helped pre-coagulation of
the wastewater. The flocs could be skimmed from
the feed tank when an operation cycle (usually 4 h)
finished. The D.C. input was 30–35 V and the corre-
38 J. Ge et al. / Separation and Purification Technology 36 (2004) 33–39

Table 1
Pilot scale field test results
Harbin, Heilongjiang Wuxi, Jiangsu Shunyi, Beijing
(24 January, 2002) (13 November, 2001) (16 March, 2002)
Influent Effluent Influent Effluent Influent Effluent

Conductivity (␮S) 1904–786 956–675 830–712 719–655 1159–897 735–589

pH 9.56–7.83 8.15–7.24 10.68–9.77 8.73–7.92 9.35–8.45 8.09–7.77
Turbidity (NTU) 583–471 12.3–8.26 78.0–32.2 11.2–10.5 810–225 4.25–1.41
COD (mg/l) 1090–785 45.6–32.4 65.9–31.8 11.2–5.3 890–628 71.2–59.3
MBAS (mg/l) 72.3–64.5 11.2–9.6 14.6–8.3 2.9–1.7 72.5–57.6 8.9–5.8
Number of samples: 6.

sponding current was about 30A. ACD was employed References

to alleviate the passivation of the electrodes and the
time interval was 15 min.
The field test results are shown in Table 1. As for
the laundry wastewater of Shunyi (Beijing), when
poly aluminum chloride (10% Al2 O3 ) was used, the
dosage was 1200 mg/l, equal to 63.5 mg/l Al3+ ,
to achieve the same residual turbidity. The settled
sludge amounted to nearly 40% of the total vol-
ume. For the electrochemical process (32V/30A,
1.5 m3 /h), the Al3+ consumption was 6.72 mg/l.
Table 1 also indicated that the pH of the treated
wastewater was neutralized and the electrical con-
ductivity reduced. The latter distinguished the bipolar
electrocoagulation–electroflotation process from other
coagulation/flotation processes.
5. Conclusion
A new bipolar electrocoagulation–electroflotation
process was developed for the treatment of laundry
wastewater. The process successfully removed turbid-
ity, COD, phosphate and MBAS simultaneously in
the pH range of 5–9. The laboratory results showed
that the removal of COD was greater than 70%.
And the removal efficiencies of MBAS, turbidity and
P-phosphate could be reached above 90%. The 1.5
m3 /h pilot scale tests proved that the process was
competitive for the treatment of laundry wastewater.
Acknowledgements
The research was financially supported by National
Outstanding Youth Fund (No. 50225804).
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