This article was originally published in a journal published by

Elsevier, and the attached copy is provided by Elsevier for the

authors benefit and for the benefit of the authors institution, for
non-commercial research and educational use including without
limitation use in instruction at your institution, sending it to specific
colleagues that you know, and providing a copy to your institutions
administrator.
All other uses, reproduction and distribution, including without
limitation commercial reprints, selling or licensing copies or access,
or posting on open internet sites, your personal or institutions
website or repository, are prohibited. For exceptions, permission
may be sought for such use through Elseviers permissions site at:

http://www.elsevier.com/locate/permissionusematerial
 Separation and Purification Technology 54 (2007) 388395

Electrochemical coagulation for oily water demulsification

py
Chen-Lu Yang
Environmental Chemistry Laboratory, Advanced Technology and Manufacturing Center,
University of Massachusetts-Dartmouth, Fall River, MA 02723, United States

co
Received 20 July 2006; received in revised form 17 October 2006; accepted 19 October 2006

Abstract
Motor oil and industrial surfactants were used to prepare synthetic oily water. When stabilized with surfactant, the turbidity shows a positive
correlation with the oil content in the emulsion with a correlation coefficient of 1.78 FAU/(mg/L). The oilwater emulsion was tested with gravity

al
separation, centrifugation, flotation, and electrochemical coagulation for the effectiveness of each process on demulsification. Electrochemical
coagulation was then selected for further study. A dc voltage was applied to the electrodes, dissolving ferrous ions (Fe(II)) at the anode and forming
hydrogen (H2 ) gas and hydroxyl (OH ) ions at the surface of the cathode. A few 100 mg/L of sodium chloride (NaCl) were added to the solution to
provide ionic conductivity and to prevent passivation of the iron electrode. The ferrous ions were oxidized into ferric ions (Fe(III)), destabilizing
on
the emulsion. The coalesced oil droplets were adsorbed into the highly dispersed and reactive ferric hydroxide (Fe(OH)3 ) coagulant. The oil-rich
sludge that was generated in the operation was then floated to the surface forming a blanket that was removed by skimming. This complicated
mechanism was completed in 4 min. When the reactor was operated for this amount of time, a measure of 165.8 mg/L of ferric ions was generated.
The treatment reduced the turbidity of the emulsion from 1800 to 60 FAU. Beyond the 4-min treatment period, the addition of more iron to the
rs

system resulted in turbidity change at a much slower rate. When the operation occurred continuously with a current of 2 A and a throughput of
320 mL/min, the turbidity of the electrically treated effluent was less than 14 FAU, the detection limit of the Hach DR/4000 Spectrophotometer.
2006 Elsevier B.V. All rights reserved.
pe

Keywords: Electrochemical coagulation; Oily wastewater; Demulsification; Emulsion; Turbidity; Anodic dissolution

1. Introduction ily during the slaughtering, cleaning, and by-product processing

phases. The grease content in meat packinghouse wastewater
Oily wastewater has remained problematic in various indus- may run several 1000 mg/L.
r's

tries for decades. Major industrial sources of oily wastewater
include petroleum refining, metals manufacturing and machin-
ing, and food processing. The American Petroleum Institute
(API) has exerted a great deal of effort to develop processes
o
Currently the treatment of oily wastewater applies a primary
treatment to separate the floatable oils from the water and emul-
sified oils. A secondary treatment phase is then required to break
the oilwater emulsion and separate the remaining oil from the

to treat oily wastewater. Based on design parameters published water. Primary treatment takes advantage of the differences in
by the American Petroleum Institute, the standard instrument in the specific gravities of the oils and grease and the water. This
th

refinery waste treatment is the API Separator, although effluents
from this unit may still contain 400500 mg/L of oil.
The wastewater of metal working processes contains grind-
ing oils, cutting oils, lubrication fluids, and coolant oilwater
Au
treatment process normally involves retaining the oily wastewa-
ter in a holding tank while allowing gravity separation of the oily
material, which is subsequently skimmed from the wastewater
surface. The effectiveness of a gravity separator is dependant

emulsions with a possible soluble and emulsified oil content
that varies from 100 to 5000 mg/L. In the third major source of
oily wastewater, the food processing industry, the processing of
meat, fish, and poultry produces oil and fatty materials primar-
Tel.: +1 508 910 9857; fax: +1 508 999 9120.
E-mail address: cyang@umassd.edu.
upon a proper hydraulic design and wastewater retention time.
Short retention times of less than 20 min result in a less than
50% oilwater separation. In addition to the API separator, two
other gravity separators, both referred to as plate separators, can
be used in this phase. They are the corrugated plate interceptor
(CPI) and the parallel plate inceptor (PPI).
The other primary treatment process is dissolved air flotation
(DAF), which is normally considered a secondary level of

1383-5866/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2006.10.019
 C.-L. Yang / Separation and Purification Technology 54 (2007) 388395
treatment technology. In order to assure maximum effective-
ness, it is necessary to incorporate chemical coagulation and
flocculation [1]. The chemical treatment aspects of DAF are
extremely important with respect to the removal of colloidal or
emulsified oil.
Unlike primary treatment, which consists only of gravity sep-
aration plus skimming, any of the secondary treatment processes
are directed toward breaking the oilwater emulsion that has
been passed through the primary separator and separating the
demulsified oil from the water phase. Emulsions may be broken
by chemical, physical, or electrical methods.
Chemical methods are the most widely used in the treatment
of oily wastewater. Chemical treatment of an emulsion is usually
directed toward the destabilization of the dispersed oil droplets
or the destruction of emulsifying agents present in a first stage
followed by the removal of the separated oil. Although other
coagulants are under development, ferric and aluminum salts are
still the most widely used agents for demulsification. The process
usually consists of rapid mixing the coagulant chemicals with
the wastewater followed by flocculation and flotation or settling.
Physical methods include heating, centrifugation, precoat fil-
tration, ultrafiltration, and membrane process. Ultrafiltration and
on
membrane processes have been actively pursued [2,3] since the
Navy and Coast Guard funded development studies two decades
ago. These processes are based on the sieving action of poly-
meric membranes to control the flow of molecules or particles
rs
larger than the membrane pores. In a study conducted to visual-
ize the filtration phenomena, Matsumoto et al. [4] found that the
compressible emulsion particles broke through the microchan-
nels with increasing operating pressure while a bakers yeast
pe
deposited at the entrance of the microchannels. This makes the
selection of the membrane and operation of the ultrafiltration
system difficult for oily wastewater applications.
Tedious chemical methods and troublesome filtration pro-
cesses provided an incentive to explore other alternatives.
Electrochemical processes to treat oily wastewater were first
r's
described in patent literature in 1903, where the process
described was operated with a voltage of about 150 V and rel-
atively high current. In the early 1980s, a team of researchers
in Ford Motor Co., Dearborn, MI, was able to operate a newly
designed electrochemical reactor at voltages of about 15 V and
o
a current density of less than 10 mA/cm2 . Through years of
research, a pilot-scale system was constructed and tested in a
th
manufacturing plant that represented highly varied machining
operations [5]. The system was able to reduce the turbidity of
the incoming oily wastewater from 2500 NTU (Nephelometer
Au
Turbidity Unit) to less than 5 NTU with a power consumption
of about 6 kW h/1000 gal. However, due to a misunderstanding
in the demulsification mechanism, the system was designed to
provide a plug-flow retention time of 4 h, which was thought
to be necessary to complete the Fenton reactions in the electro-
chemical reactor used to oxidize the organic substrates.
Since then, electrochemical methods for wastewater demulsi-
fication have become an active area of research and development
[610]. A thorough review on electrochemical technologies for
industrial wastewater treatment has been done by Chen [11]. In
general, electrodeposition is effective for heavy metal recovery
389
while electrochemical coagulation is widely applied for ions,
both cations and anions, removal and demulsification. Elec-
troflotation involves the electrolytic generation of bubbles that
can be used to attach pollutants such as sludge and fine particles
and carry them to the top of the solution. As in DAF, frothers
and collectors are needed to enhance the separation efficiency of
electroflotation. In a laboratory demonstration, Ibanez and col-
leagues demonstrated that the oilwater emulsion was actually
broken down by the charge neutralization of ferric ions (Fe(III))
py
generated by the anodic dissolution of the iron electrode [12].
The sunflower-seed oil and water emulsion was clarified within
minutes of electrochemical treatment. With the mechanism in
mind, a parallel-plate electrochemical reactor was designed and
co
constructed to provide a treatment time of 220 min with intense
iron dissolution. The research presented in this paper is devoted
to better understanding the demulsification mechanism and to
acquire design and operating parameters that bring the electro-
chemical process one step closer to commercialization.
2. Demulsication mechanism
al
When direct current is applied to water through a pair of
electrodes, the energy barrier is overcome, and water molecules
are broken down into hydrogen and oxygen gases. The reac-
tion is observed through the hydrogen bubbles that evolve from
the cathode and oxygen bubbles that originate from the anode.
However, when the anode is made of metals that have lower oxi-
dation potentials than water, the anode is dissolved to produce
metal ions instead of generating oxygen. These ions then react
with hydroxyl ions, the by-products of hydrogen generation, to
produce metal hydroxides.
An electrochemical reactor is a holding tank with two sets
of iron electrodes, anodes and cathodes. The electrodes are sit-
uated a few millimeters apart from each other and submerged in
the wastewater that is to be treated for oil contamination. The
cathodes and anodes are connected to the negative and positive
outlets of a dc power supply, respectively. During electrolysis
in wastewater treatment, the sacrificial iron anode is oxidized
into Fe(II) (ferrous) ions that are further oxidized to Fe(III) ions
[11]:
O2
Fe(s) Fe(aq) 2+ + 2e Fe(aq) 3+ + e ,
air
2H2 O + 2e H2(g) + 2OH(aq) ,
Fe(aq) 3+ + 3OH(aq) Fe(OH)3(s)
As the operation progresses the ionic strength of the wastew-
ater increases. Fig. 1a shows how the oil droplets are stabilized
by the surfactant by forming micelles in aqueous solutions.
Fig. 1b shows that the electro-generated cations with their high
charges effectively neutralize the surface charges on the sur-
factant molecules. Simultaneously, hydrogen is formed at the
cathode.
The pH of the wastewater rises because of this electrochemi-
cal process. The net result of the reactions is that the emulsion is
destabilized, and the colloidal oil particles begin to coalesce, as
shown in Fig. 1b. Ultimately, the destabilized oil droplets absorb
390 C.-L. Yang / Separation and Purification Technology 54 (2007) 388395

3. Experimental

Synthetic oilwater emulsions were prepared by adding 1 g

of SAE 10W-40 motor oil (Mobil Oil) to 1 L of tap water. During
the mixing, 1.5 g of sodium chloride, NaCl (Aldrich Chemical)
and 10 mL of 5% Legsolve (Walter G. Legge Co.) were slowly
added to the mixture. Legsolve is a widely used industrial deter-
gent containing EDTA (ethylenediamine tetracetic acid), tail oil
fatty acid, sodium metasilicate, triethanolamine lauryl sulfate,

py
and diethyleneglycol monoethyl ether as the major ingredients.
While the oil was added to the mixture, samples were taken
to establish the correlation between oil content and turbidity.
Turbidity was measured with a DR/4000 Spectrophotometer

co
from the Hach Company. An analytical program (Hach 3750)
was developed for testing turbidity in water, wastewater, estu-
ary water, seawater, and industrial process water. Results were
given in Formazin attenuation units (FAU), and the estimated
detection limit for Program 3750 is 14 FAU.
Fig. 2 is the flow diagram of the bench-scale electrochemical

al
system. The system consists of a dc power supply, power regula-
tion and measurement unit, reservoir, feed pump, flow regulation
and measurement unit, and a electrochemical reactor. The reac-
on
tor is composed of acrylic plastic with the following dimensions:
16 cm long, 6.7 cm wide, and 9.2 cm deep. Taking into account
the space occupied by the equalizer at the bottom of the appa-
ratus and the siphon system on the top, the actual volume of
the reactor is 616 cm3 . The electrode sets (anode and cathode)
rs

each consist of five pieces of cast iron that are situated approx-
imately 4 mm apart and submerged in the solution. Normally,
the reactor is operated in monopolar mode, which means that all
pe

Fig. 1. The stabilization of an oilwater emulsion by a surfactant (a), and the

destabilization of emulsion by cations and the coalescence of oil droplets (b).
into the highly dispersed ferric hydroxide colloid formed by
the reaction between the electro-generated Fe(III) and hydroxyl
ions. Finally, the oil-rich sludge floats to the top where it is
removed by skimming.
r's
the electrodes are physically connected to either the positive or
the negative outlet of the dc power supply. By subtracting the
volume occupied by the two electrode sets, the active volume of
the reactor is 560 cm3 .
For continuous operation, a synthetic oilwater emulsion was
prepared and stored in the reservoir for a few minutes to allow

the free oil to float to the top of the solution. The emulsion was
o
th
Au

Fig. 2. The flow diagram of the bench-scale electrochemical system.

 C.-L. Yang / Separation and Purification Technology 54 (2007) 388395
then pumped into the reactor to examine the effectiveness of the
major operating parameters (current density, treatment time, oil
content and flow rate) on demulsification. The effectiveness of
each parameter was determined by the differences in turbidity
between treated and untreated emulsions.
4. Results and discussions
The synthetic oilwater emulsion was tested by gravity
separation, centrifugation, electroflotation and electrochemical
coagulation. Among these treatment methods, electrochemical
coagulation was very effective in demulsification and was
selected for further study.
4.1. Turbidity
A set of experiments was conducted to establish the corre-
lation between the oil content in the emulsion and its turbidity.
Liquid samples were taken to determine the turbidity while oil
drops were added to the mixture. Fig. 3 shows that without sur-
factant in the emulsion, the ratio of turbidity and oil content
decreased from 2.39 to 0.66 when oil content increased from
100 to 1000 mg/L. According to the BeerLambert Law, a lin-
on was detected in the following 15 min. Any meaningful experi-
ear relationship between absorbance and concentration can be
expected from a real solution. It is believed that the dispersed
oil droplets collide and form bigger droplets at high oil con-
tent to deviate the optical behavior of the emulsion from that
rs
of a real solution. Fig. 3 also displays that a linear relationship
can be established between oil content and turbidity when trace
amount of Legsolve is added to the oilwater emulsion. When
pe
the emulsion is stabilized by Legsolve, turbidity was found to
have a positive correlation with the oil content in the emulsion
with a correlation coefficient of 1.78 FAU/(mg/L).
4.2. Gravity separation and emulsion stability
Immediately after mixing, the emulsion of 1000 mg/L of oil in
r's
water had a turbidity of 1430 FAU. A portion of the emulsion was
transferred to a separation funnel to evaluate its stability against
gravity. Samples were taken from the center of the separation
funnel every 5 min to determine the turbidity. Fig. 4 shows that
o
the motor oilwater emulsion is relatively stable at an oil content
th
Au
Fig. 3. The correlation between oil content and turbidity.
391
py
co
Fig. 4. The stability of motor oil in water emulsions.
of about 1000 mg/L. The turbidity slowly decreased from 1430
to 1315 FAU in 50 min. After that, the readings began to show
perturbations. Since the emulsion was prepared by mechanical
stirring, it seems that the oil droplets began to coalesce after
al
stagnating for 50 min in the separation funnel. An 8% decrease
was observed in the first 50 min while another 13% decrease
ments concerning the mechanical emulsion must therefore be
completed within 50 min in order to avoid significant errors
associated with the instability. Without coagulant, a gravity sep-
aration unit will not be effective for the motor oilwater emulsion
generated by mechanical stirring.
The stability test was repeated with 0.5 mL of Legsolve in
one liter of oilwater emulsion. The surfactant stabilized the
emulsion system by creating smaller micelles in the mixture.
The smaller micelles also contributed to a higher turbidity read-
ing. The emulsion of 1000 mg/L of oil in water experienced a
turbidity increase from 1430 to 1780 FAU due to the addition
of surfactant. After stagnating in a separation funnel for 1 h, the
turbidity of the mixture was still around 1800 FAU.
Since ionic conductivity is crucial for electrochemical pro-
cesses, a trace amount of sodium chloride (NaCl) was added
to increase the conductivity of the mixture. NaCl was selected
because of the high mobility of the sodium ions and the benefit
of depassivation from the chloride ions. However, since sodium
ions carry positive charges, they may destabilize the emulsion
and cause errors in the determination of the treatment efficiency.
One liter of oilwater emulsion was prepared by mixing 1 g of
motor oil with 0.5 g of NaCl and 0.5 mL of Legsolve in 1 L
of tap water. After vigorous stirring for 1 min, the mixture was
then transferred to a separation funnel for the stability test. As
done before, samples were taken to determine the turbidity. The
results show that NaCl increases the turbidity of the mixture
although the contribution is marginal. The results also indicate
that the 196 mg of sodium ions in the mixture do not destabilize
the surfactant-stabilized oilwater emulsion.
4.3. Centrifugation
Immiscible liquids and suspended particles are separated
industrially in centrifugal decanters. The separating force is
392 C.-L. Yang / Separation and Purification Technology 54 (2007) 388395
Fig. 5. The change of turbidity after the emulsion is subjected to centrifugation
for 10, 15, 30, and 60 s.
much larger than that of gravity and it acts in the direction oppo-
site to the axis of rotation instead of downward. A set of exper-
iments was conducted to evaluate the feasibility of centrifugal
force for separation of oil and water from emulsified aqueous
solutions. A Cole Parmer 17250-10 Fixed Speed Centrifuge was
used to provide a relative centrifugal force of 1318 g. Samples
were prepared by mixing 1 g of motor oil in 1 L of tap water with
0.6 g of NaCl. After mixing for 1 min, the oilwater emulsion
had an initial turbidity of 1332 FAU. Fig. 5 shows the change
of turbidity after the emulsion is subjected to centrifugation for
rs
10, 15, 30, and 60 s. Turbidity dropped about 50%, from 1332
to 720 FAU in the first 15 s and stabilized at 410 FAU. Instead
of settling on the bottom of the test tube, a layer of oil floated to
pe
the surface of the liquid after the centrifugation. Low oil content
emulsions are stable even under a strong centrifugal force.
4.4. Electroflotation
Another physical separation method that is widely used in the
r's
mining industry for particle separation is flotation. In flotation,
small air bubbles released from the solution attach themselves
to suspended particles. The airsolid mixture rises to the sur-
face of the solution where it concentrates and is removed. In
electroflotation, an electric version of flotation, bubbles are gen-
o
erated predominately by the electrolysis of water. Instead of
air, hydrogen and oxygen bubbles are generated to perform the
th
binding function.
An electroflotator was constructed to study the feasibility of
this method for separating oil from water in an emulsified solu-
Au
tion. The cell was designed to have evenly distributed bubbles
evolve from the bottom of the cell so that the bubbles have max-
imum contact time with the sludge or fine particles suspended
in the solution. In electroflotation, the gas bubbles are generated
electrically in the cell. A pair of closely spaced (2 mm apart),
horizontal electrodes was placed towards the base of the cell
to cover the whole area. The cathode is made of stainless steel
gauze while the anode is a piece of graphite sheet from Becker
Brothers Carbon Copr., Cicero, IL. A sample of 250 mL was
tested in the cell each time. The cell was operated at a dc volt-
age of 16 V. The voltage was able to draw a current of 400 mA
py
co
Fig. 6. The turbidity change when the emulsified solution was treated in the
electroflotator.
in the cell. The emulsified solutions were prepared by mixing
1 g of motor oil and 0.6 g of NaCl in 1 l of tap water. The ini-
tial turbidity of the solution was 1509 FAD. When 10 mL of
al
10% Legsolve was added to the solution, the turbidity increased
to 1871 FAU. It is believed that the change in turbidity is due
on
to the stabilization of the oilwater micells by the surfactant.
Interestingly, it took only 8 V to draw a current of 400 mA in
the cell when Legsolve was added to the solution. Fig. 6 shows
the turbidity change when the emulsified solution was treated
in the electroflotator. In both cases, with and without surfactant,
electroflotation reduced the turbidity by about 40%. During the
operation, micelles were brought to the surface of the solution
by electrically generated bubbles but none actually accumulated.
Therefore, a frother is needed for electroflotation to be effective
for oilwater separation.
4.5. Electrochemical coagulation
Motor oil has a density lower than water, thus free oil will
float to the surface of the solution. However, in the emulsified
oily water, the oil is stabilized by the formation of micelles with
surfactant. Flotation carries the micelles to the surface of the
solution but is not able to detain the oil unless the emulsion is
destabilized. Multivalent metal ions, such as ferric ions, are used
widely to demulsify oilwater emulsions.
One way of generating metal ions in an electrochemical reac-
tor is through anodic dissolution of sacrificial electrodes. A set
of experiments was conducted to study the applicability of ferric
ions for oily water demulsification, using a set of cast iron sheets
as the sacrificial anode. Synthetic oilwater emulsion was pre-
pared by mixing motor oil with tap water, and a trace amount of
NaCl was added to provide conductivity. As expected, a signifi-
cant amount of brown sludge was generated when 1 A of current
was passed through the cell. Samples were taken from the cell
along the treatment timeline to determine the turbidity. Fig. 7
shows the change in turbidity when the oilwater emulsion is
subjected to electrochemical treatment. The turbidity of the syn-
thetic emulsion dropped from 1380 to 160 FAU in a treatment
time of 6 min. With a current of 2 A, the turbidity dropped further
to 43 FAU.
 C.-L. Yang / Separation and Purification Technology 54 (2007) 388395
Fig. 7. The change in turbidity when the oilwater emulsion is subjected to
electrochemical treatment.
During the electrolysis, ferric ions were generated on the
surface of the anode at the same time hydroxyl groups and some
hydrogen bubbles were formed at the cathode. Through mixing,
the ferric hydroxides that formed in the solution precipitated
providing a tremendous amount of surface area to absorb then
on
remove oil droplets from the aqueous phase.
Another concern with the whole process is that most of the
oily wastewaters are stabilized by surfactants. The electrochem-
ical treatment has to provide a mechanism in which to break
rs
the micelles for the coagulation to be effective in demulsifica-
tion. In this study, a small amount of surfactant was used to
stabilize the oily water and was prepared by adding 10 mL of
5% Legsolve to the synthetic oilwater emulsion. The solution
pe
was then treated in the same reactor under the same condi-
tions. Fig. 8 shows the turbidity change during the treatment.
When operated at 2 A for 4 min, the current carried 480 C of
electron charge into the reactor, generating 92.8 mg of ferric
ions in the solution, which effectively destabilized the oilwater
emulsion. In a cell of 560 mL, the Fe(III) concentration was
r's
165.8 mg/L.
o
th
Au
Fig. 9. The variations in the key parameters in the electrochemical operation.
393
py
co
Fig. 8. The effect of surfactant on turbidity change during the electrochemical
treatment.
Due to the removal of surfactant molecules from the micelles,
oil droplets were released into the aqueous phase where they
al
coalesced into larger oil drops. The oil drops attached them-
selves to the bubbles and floated to the surface of the solution
where they were eventually absorbed into the ferric hydroxide
particles. Even with the presence of Legsolve, electrochemi-
cal coagulation consistently reduced the turbidity to less than
50 FAU.
To view the effectiveness of the batch operation, a 50 L
oilwater emulsion was prepared to test the unit in a more prac-
tical, continuous mode. The solution was prepared by mixing
50 g of motor oil with 25 g of NaCl and 500 mL of 5% Leg-
solve. The mixture was then raised to a final volume of 50 L by
adding tap water. The initial turbidity was 1368 FAU, and the pH
was 8.1. At a rate of 240 mL/min, the solution was pumped into
the reactor for treatment. The variations in the key parameters
in the operation are depicted in Fig. 9. The pH increases with
operation time and is stabilized at 10 min. Initially, the volt-
age needed to draw a current of 2 A in the reactor was 6.8 V.
The applied voltage decreased along with the operation time
394 C.-L. Yang / Separation and Purification Technology 54 (2007) 388395
Fig. 10. The applied voltages in a continuous electrochemical operation.
on
rs
pe
Fig. 11. The pH in a continuous electrochemical operation.
and stabilized at 4.6 V. The effluent turbidity was always below
50 FAU.
Fig. 10 shows the applied voltages, and Fig. 11 shows the pH
at different feeding rates. Overall, the system is stable in both
r's
chemical and electrical parameters. A flow rate of 240 mL/min
represents a treatment time or residence time of 2.3 min. In
Fig. 12, a flow rate of 320 mL/min represents a treatment time
of 1.75 min, and the effluent turbidity was constantly below
o
th
Au
Fig. 12. The effluent turbidity of continuous electrochemical treatment.
14 FAU, the detection limit of the spectrophotometer. This dia-
gram demonstrates that with a flow rate of 320 mL/min, an
efficiency of more than 99% is achievable.
5. Conclusions
Oil in water can be stabilized by surfactants such as Legsolve
by forming micelles in the mixture. When stabilized with surfac-
py
tant, the turbidity of the emulsion shows a positive correlation
with oil content. A centrifugal force of 1318 g reduces about
50% of the turbidity in 1 min. Longer treatment time will not
further reduce the turbidity. Bubbles generated by electrolysis
co
carry micelles to the top of the solution but fail to detain the oil
droplets for further separation. Ferric ions are generated in the
electrochemical cell by anodic dissolution of consumable iron
electrodes. Providing the needed conductivity to the solution,
sodium chloride is essential to electrochemical coagulation oper-
ations. More importantly, the chloride is able to penetrate the iron
oxide formed on the surface of the iron electrode and effectively
al
prevents polarization from happening. The ferric ions attract sur-
factant molecules, break micelles, and release oil droplets into
the aqueous solution. The coalesced oil drops attach to bubbles
and float to the top of the solution where they are eventually
adsorbed by the coagulant. Instead of breaking down the oil,
electrochemical coagulation generates a coagulant that breaks
down the micelles and collects oil in the floating coagulant. The
treatment time is reduced from 4 h to 4 min, and the effluent
turbidity is beyond the detection limit of the spectrophotometer.
Nevertheless, the oil-rich sludge needs to be dealt with when
skimmed from the top of the solution.
Acknowledgement
The author is grateful to Alison Mello of the Department of
Chemistry and Biochemistry at the University of Massachusetts-
Dartmouth for editing this manuscript.
References
[1] R.L. Vaughan Jr., B.E. Reed, G.W. Roark, Pilot-scale investigation of chem-
ical addition-dissolved air flotation for the treatment of an oily wastewater,
Environ. Eng. Sci. 17 (5) (2000) 267277.
[2] M.J. Um, S.-H. Yoon, C.-H. Lee, K.-Y. Chung, J.-J. Kim, Flux enhancement
with gas injection in crossflow ultrafiltration of oily wastewater, Water Res.
35 (17) (2001) 40954101.
[3] M. Gryta, K. Karakulski, A.W. Morawki, Purification of oily wastewater
by hybrid UF/MD, Water Res. 35 (15) (2001) 36653669.
[4] K. Matsumoto, S. Katsuyama, H. Ohya, Cross-flow filtration of yeast by
polarization redevelopment and flux in pressure pulsed ultrafiltration, J.
Membr. Sci. 155 (1) (1999) 113122.
[5] M.H. Weintraub, R.L. Gealer, A. Golovoy, M.A. Dzieciuch, H. Durham,
Development of electrolytic treatment of oily wastewater, Environ. Progr.
2 (1983) 3237.
[6] G.H. Chen, X.M. Chen, P.L. Yue, Electrocoagulation and electroflotation
of restaurant wastewater, J. Environ. Eng. 126 (9) (2000) 858863.
[7] L. Sanchez-Calvo, G. Tanguy, M.C. Cames, G. Paternotte, G. Valentin,
A. Rostan, P. Lapicque, An electrocoagulation unit for the purification
of soluble oil wastes of high COD, Environ. Progr. 22 (1) (2003) 57
65.
 C.-L. Yang / Separation and Purification Technology 54 (2007) 388395 395

[8] N.M. Mostefa, M. Tri, Coupling flocculation with electroflotation for waste
oil/water emulsion treatment: optimization of the operation conditions,
Desalination 161 (2004) 115121.
[9] J.C. Donini, J. Kan, J. Szynkarczuk, T.A. Hassan, K.L. Kar, The operating
cost of electrocoagulation, Can. J. Chem. Eng. 72 (1994) 10071012.
[10] X. Xu, X. Zho, Treatment of refectory oily wastewater by electro-
coagulation process, Chemosphere 56 (10) (2004) 889894.
[11] G. Chen, Electrochemical technologies in wastewater treatment, Sep. Purif.
Technol. 38 (1) (2004) 1141.
[12] J.G. Ibanez, M.M. Takimoto, R.C. Vasquez, S. Basak, N. Myung, K.
Rajeshwer, Laboratory experiments on electrochemical remediation of the
environment: electrocoagulation of oily wastewater, J. Chem. Educ. 72 (11)
(1995) 10501058.

py
co
al
on
rs
pe
o r's
th
Au