CTROFLOCCULATION

S t a t e - o f - t h e - A r t Electroflocculation
J.P.F. Koren and U. Syversen
Ostfold Research Foundation, PO Box 276, N-1601 Fredrikstad, Norway
The electroflocculation principle has been known since the beginning of the century, but until
recently it has not been used in industrial applications. The 'Purifier' described in the paper is an
eleclroflocculation unit which can separate oil, organic substances and heavy metals from water. It
is most competitive with concentrations of less than 5000 parts per million oil or organic
substances in water. The paper describes the major working principles of the 'Purifier'.

iLpolluted water and water polluted with o t h e r organic

s u b s t a n c e s is a p r o b l e m in m a n y different industries.
Demands from the authorities and general public for a cleaner
environment will increase, and the authorities might reduce the
legal effluent concentrations to 20 mg of organic s u b s t a n c e s per
litre of effluent. When the effluent is characterised as hazardous
waste, it is illegal to drain it into the sewer. It might only consist of
0.5% oil, while the rest is pure water. These huge volumes of lowconcentration oily waste are expensive to treat. If the oil could be
separated from the water it would be much less costly to treat the
oily waste, because of the lower volume. The oily sludge can
probably be incinerated, and the water reused in the industrial
process with a reduction in the cost of new process water.
The electroflocculation unit is capable of separating many kinds
of organic substances and heavy metals in addition to oil. The
degree of separation is in most cases above 99%, and the power
c o n s u m p t i o n is about 1 kWh/m 3 of wastewater. Current units can
treat about 1 m:3/h of wastewater in a continuous process. The best
results are when the wastewater contains 5000 p p m organic
substances or less.

History
Electrolytic processes to separate oil in wastewater were described
in the p a t e n t literature as early as 1903. The process was used to
txeat condensed water from steam engines, before it entered the
steam boiler as feedwater. The unit used iron sheets as the anode
material; the iron was oxidised during the process, and had to be
replaced after a while. The electrolysis cell o~erated with a
potential of 150 V and with a fairly high current. [ ]
This process was f u r t h e r developed by Weintraub, Gealer
Golovoy and Dzieciuch into a continuous process to clean oily
wastewater from metal-cutting, forming, rolling and finishing
~,perations. An electrolytic cell which can treat 3.8 1/min of
wastewater was designed and patented in 1980. The wastewater
which was fed into the unit contained from 300 to 7000 mg oil/litre
of water. The processed water contained less than 50 mg/l for 90%
,)f the time, and less than 25 mg/l for 83% of the time. The unit can
be improved to reach an effluent oil concentration of 10 mg/l. The
power consumption was calculated to be 1.6 kWh/m3. I11
One of the first e x p e r i m e n t s with electroflotation was in 1911,
1reating domestic sewage in the United States. This m e t h o d has not
become generally used because the electrodes tended to scum after
a while and, because of this, the efficiency decreased with time. [21
Flotation processes are used extensively in the mining industry,
In 1904, it was p r o p o s e d for the first time to use electrolysis to
make gas bubbles to 'float' minerals. The process was used in some
mines in Broken Hill, Australia. However, the operation was not
successful, because the power c o n s u m p t i o n was too high and
because the technology was not well enough developed. [al
In 1946, Rivkin et al. [31 obtained a p a t e n t for a m e t h o d for
(,lectroflotation of ore. They designed several laboratory-scale
~,lectroflotation cells, which gave an improved flotation rate
( o m p a r e d to other flotation techniques. This m e t h o d is not
r e p o r t e d to have been taken into c o m m e r c i a l u s e by t h e
industry. [a] Other e x p e r i m e n t s with electrolytic cells have been
reported, but it a p p e a r s t h a t electroflotation of minerals is still at
the laboratory/experimental stage. This is because only a limited
a m o u n t of research has been done on the m e c h a n i s m s and the
design of the cell. lal
Kaliniichuk et al. have described an electroflocculation unit
which can be used to separate an oil-in-water emulsion. 14] They
achieved a degree of separation of more t h a n 99% with a power

Filtration & Separation

February 1995

c o n s u m p t i o n of 0.48 kWh/m 3 of water, but thcy used a residenc(.

time of 10--20 rain. [41

Electroflotation
In flotation processes, air or gas is bubbled t h r o u g h a liquid
containing particles which float or are emulsified in the water, The
process consists of four basic steps: (1) gas bubble generation, (2)
c o n t a c t between gas b u b b l e and oil drop, (3) gas bubble
adsorption on the surface of the particle and (4) the gas bubbles
and oil d r o p s rising to the surface. ['~] At the surface a layer of foam
will be created. This foam consists of gas bubbles and the flotated
particles, and can be removed by skimming. The rate of flotation
d e p e n d s on several parameters, such as the surface tension
between the water, particles and gas bubbles; the gas bubble
diameter; the size of the particles; the water's residence time in the
electrolytic cell and the flotation tank; the particle and gas bubble
zeta potentials; and the temperature,*-pH and particle size
distribution.
There are many different flotation methods. The conventional
process is to use a c o m p r e s s o r to btow air t h r o u g h nozzles in the
b o t t o m of the flotation tank. The problem is the distribution of the
air bubbles, and to make small enough bubbles. Small gas bubbles
are more efficient t h a n larger gas bubbles, since they have a larger
surface area per unit volume of gas. Smaller gas bubbles also have
the advantage t h a t they have lower buoyancy, and so will have a
longer residence time in the electrolyte. This increases the
possibility for collisions between bubbles and oil particles.
A n o t h e r m e t h o d is dissolved-air flotation, which gives a better
bubble distribution in the water. The disadvantages is t h a t it is not
a continuous process, and it is difficult to control the bubble flux.
During the process air is injected into the water u n d e r pressure;
when the p r e s s u r e is released, the water is s u p e r s a t u r a t e d with air,
which is released as air bubbles. I6] This is the same process t h a t
h a p p e n s when a bottle of carbonated water or beer is opened.
A method which follows the same principle, but which uses a
very low pressure, is v a c u u m flotation. The water is saturated with
air at atmospheric pressure, and when a vacuum is applied, air
bubbles will be released. 16] This process has the same advantages
and disadvantages as dissolved-air flotation.
Electroflotation is a continuous method. The bubbles are
generated by electrolysis of water; the water flows between two
electrodes, and is reduced to hydrogen at the cathode and oxidised
to oxygen at the anode. One advantage is t h a t the gas bubbles
generated are essentially at the same, very small size. However, the
power c o n s u m p t i o n can be high if the process is not well designed
and optimised. A n o t h e r advantage is that it is easy to adjust the
gas bubble flux, by varying the current across the electrodes. The
distribution of the gas bubbles is also good, because the bubbles
are produced over the whole area of the electrode.

Electropreoipitation
Electroprecipitation is a flocculation process where the flocculating agent is ions of metal which are precipitated from the anode.
The metal ions will settle in the electrolyte, but on the way down
they collide with particles in the electrolyte, and adsorb onto the
surface of these particles. The best anode material is iron or
aluminium, because they give trivalent ions; m o s t o t h e r cheap and
easy accessible metals give bivalent ions. Trivalent ions have a
higher ability to adsorb onto particles in the water than bivalent
ions, because they have a higher charge density.
The m e c h a n i s m which breaks down emulsions in the water
p h a s e is not fully understood. Weintraub et al. suggested t h a t the

0015-1882/95/US$7,00 ~ 1995 Elsevier Science Ltc~

153

CTROFLOCCULATION
b r e a k d o ~ of e m u l s i o n s is b r o u g h t a b o u t with t h e a s s i s t a n c e of
hydroxyl r a d i c a l s w h i c h are g e n e r a t e d d u r i n g ferrous-ion oxi da tion. The r e a c t i o n s e q u e n c e is:
Fe 2+ + 0 2 + H +

Fe 2+ + H O ' 2 + H ~ =
Fe 2+

Fe e~

Fe a+ + HO2
Fe '~+ + H202

HzOz - - ~ Fe n+ + HO + O H HO

- - ~ Fe 3~ + OH ~

(a)
(b)
(c)
(d)

The f e r r o u s i o n / h y d r o g e n p e r o x i d e s o l u t i o n t a k i n g p a r t in
r e a c t i o n s (c) an d (d) is r e c o g n i s e d as F e n t o n ' s reagent, a n d is a
powerful o x i d i s i n g system. The e m u l s i o n is d e s t a b i l i s e d by b o t h
o x i d a t i v e d e s t r u c t i o n of t h e c h e m i c a l e m u l s i f i e r a n d by n e u t r a l i s a tion of t h e e m u l s i o n / d r o p l e t charge. TM
No m e c h a n i s m h a s been s u g g e s t e d w i t h a l u m i n i u m as t h e
anode. A l u m i n i u m ions are very unstable, a n d it is s u g g e s t e d t h a t
a l u m i n i u m ions reac t with hydroxyl ions a n d m a k e a n e t w o r k as
soon as t h e y are r e l e a s e d from t h e anode. The n e t w o r k of
a l u m i n i u m h y d r o x i d e will a d s o r b onto colloidal particles. Collob
dal p a r t i c l e s are defined as p a r t i c l e s which in t h e d i s p e r s e d s t a t e
have an e x t e n s i o n in at l e a s t one d i m e n s i o n of between 1 nm a nd 1
Hm. The u p p e r l i m i t is not distinct, since p a r t i c l e s which a re l a r g e r
t h a n 1 Hm are also t r e a t e d as colloidal p a r t i c l e s if t h e y have
p r o p e r t i e s like colloidal particles. 17]
The n e t w o r k of a l u m i n i u m ions is built up from a c h a i n w i t h
t h r e e hydroxyl ions p e r a l u m i n i u m ion. The c h a i n s can be several
h u n d r e d ~ n g s t r o m s long, b u t only a few p a r t i c l e d i a m e t e r s thick.
The c h a i n s are c r e a t e d by a c o n d e n s a t i o n p o l y m e r r e a c t i o n
m e c h a n i s m . The p r o c e s s d e p e n d s on pH a n d t e m p e r a t u r e to c r e a t e
the correct crystals. At 25C the pH in t h e w a t e r m u s t be between 4
and 10, a n d at 100('C between 3 and 7, in order to cr e a t e l a rge
cKystals. O u t s i d e t h e s e pH r a n g e s the a f u m i n i u m ions will re a c t to
make less c o m p l e x c o m p o u n d s with hydrogen a n d oxygen. [s]

Electroflocculation
E l e e t r o f l o c c u l a t i o n is a c o m b i n a t i o n of the p r o c e s s e s of electroflotation a n d e l e c t r o p r e c i p i t a t i o n . Our e l e e t r o f l o e c u l a t i o n u n i t
c o n s i s t s of an electrolytic cell with an a l u m i n i u m a n o d e a n d a
s t a i n l e s s - s t e e l cathode. The a n o d e m u s t be more easily o x i d i s a b l e
than the c a t h o d e to give t h e correct effect. B a l m e r a n d F oul ds [1
tried m a n y different e l e c t r o d e m a t e r i a l s , such ms iron, steel, copper,
brass, zinc, alloys of a l u m i n i u m , bronze a n d p h o s p h o r bronze. All of
~hese m a t e r i a l s p r o d u c e d e n o u g h flocs, and gave a high degree of
s e p a r a t i o n . They concluded t h a t t h e c h e a p e s t a n d m o s t easily
accessible electro de m a t e r i a l s s h o u l d be used.
An electrolytic cell can be d e s i g n e d in m a n y different ways. [m}
Here we will d i s c u s s a specific unit, which h a s been d e s i g n e d a n d
p a t e n t e d by J a n Sundell; t h i s u n i t is called the 'Purifier'. The
d i s t a n c e between t h e e l e c t r o d e s is 3 ram; t h i s d i s t a n c e is an
i m p o r t a n t d e s i g n v a r i a b l e w h e n it c o m e s to o p t i m i s i n g t h e
~Jperating costs of t h e unit. The o p e r a t i n g costs are d e p e n d e n t on
l he p o w e r c o n s u m p t i o n , which can be e x p r e s s e d as
P

U x I

(1)

where P is the power c o n s u m p t i o n (W), U is the voltage IV) a n d I

is the c u r r e n t (A). Using Ohm's Law (U = / ~ I, where /~ is t he
r e s i s t a n c e in o h m s ) , it is also p o s s i b l e to rewrite Eqn. 1 as
P =
P

R [2

(2)

U~
= ~

(3)

The r e l a t i o n s h i p between c u r r e n t a n d power c o n s u m p t i o n is s how n

in Eqn. 2, a n d a c h a n g e in c u r r e n t will c h a n g e t h e pow e r
c o n s u m p t i o n in the second power. The a m o u n t of gas w h i c h
evolves at the e l e c t r o d e s is d e p e n d e n t on t h e c u r r e n t flowing a c ros s
he electrodes.
To reduce t h e p o w e r c o n s u m p t i o n w i t h o u t c h a n g i n g th e c u r r e n t
and t h e degree of s e p a r a t i o n , one can reduce the r e s i s t a n c e in t h e
electrolyte. R e d u c i n g t h e d i s t a n c e between t h e e l e c t r o d e s or
increasing t h e c o n d u c t i v i t y of t h e electrolyte will reduce t he p o w e r
, . onsu mp tion w i t h o u t c h a n g i n g t h e degree of s e p a r a t i o n , b e c a u s e
he c u r r e n t is not changed. Ohm's Law s t a t e s t h a t t h e pow e r
c o n s u m p t i o n will d e c r e a s e ms t h e d i s t a n c e between t h e e l e c t r o d e s
is r e d u c e d an d as t h e c o n d u c t i v i t y of the electrolyte increases.
The eleetrolyte's c o n d u c t i v i t y will affect t h e p o w e r c o n s u m p t i o n
in t h e s a m e way as the d i s t a n c e between t h e electrodes. Ac c ordi ng
to Ohm's Law, a high c o n d u c t i v i t y in t h e electrolyte a n d a s m a l l
154

d i s t a n c e be t w e e n t h e e l e c t r o d e s gives a low p o w e r c o n s u m p t i o n . I'1

In s o m e t ype s o f w a s t e w a t e r t h e c o n d u c t i v i t y is too low, a n d it is
n e c e s s a r y to a d d s o m e s a l t s to i n c r e a s e t h e n u m b e r of dissolved
ions in t h e electrolyte. The s i m p l e s t m e t h o d is to a d d t a b l e salt
(NaGl), b u t it h a s a l s o been r e p o r t e d t h a t 0.01N CaC12 h as been
used to i n c r e a s e t h e c o n d u c t i v i t y of t he electrolyte. U]
There is an o p t i m u m a r r a n g e m e n t w i t h a c e r t a i n power
c o n s u m p t i o n a n d a c e r t a i n d e g r e e of s e p a r a t i o n . When t h e c u r r e n t
in t h e electrolytic cell is increased, t h e ga s bubbl e flux increases;
t h i s i n c r e a s e s t h e s e p a r a t i o n effect. However, w h e n t h e co n cen tr ation of ga s b u b b l e s is increased, t he p o s s i b i l i t y t h a t two gas b u b b l e s
collide a l s o increases. This r e d u c e s t h e s e p a r a t i o n effect since
l a r g e r gas b u b b l e s are less effective t h a n s m a l l e r gas bubble:r,
b e c a u s e t he y have a s m a l l e r surface a r e a / v o l u m e ratio. In a d d i t i o n ,
gas b u b b l e s have a lower c o n d u c t i v i t y t h a n t h e electrolyte; t h i s
i n c r e a s e s t h e pow e r c o n s u m p t i o n .
When t h e gas bubbl e c o n c e n t r a t i o n increases, t h e r e s u l t is t h a l
t he degree of s e p a r a t i o n i n c r e a s e s as t h e c u r r e n t i n c r e a s e s up to ~
c e r t a i n level. The c o n c e n t r a t i o n of t h e ga s b u b b l e s gives a large
c o n t r i b u t i o n to t h e electrolyte resistance, a n d e v e n t u a l l y too m an y
of t he gas b u b b l e s will coalesce. The de gre e of s e p a r a t i o n will th en
slowly d e c r e a s e as t he c u r r e n t a c ros s t h e e l e c t r o d e s increases. U~I
At a c e r t a i n point, i n c r e a s i n g t h e pow e r c o n s u m p t i o n will no longer
affect t h e degree of s e p a r a t i o n .

T h e e l e c t r o d e reactions
The a n o d e a n d c a t h o d e r e a c t i o n s are a s follows:
2H20 + 2e - =

H2(g) + 2OH

(cathode) E = -0.83V

2H~O = Oz(g) + 4H + + 4 e -

(anode)

E =

Alia) = Al 3+ + 3e

(anode)

E = -- 1.66

2Alia) + 6 H 2 0 = 3H2(g) + 6 O H

+ 2 A I :~+ (Total)

+0.40V

E = +0.83 \

Hydrogen gas will evolve on t h e cathode, a n d oxygen gas will evolve

on t he anode; oxygen gas will only evolve a t high c u r r e n t d e n s i t i e s
It is a n a d v a n t a g e t h a t hydroxyl ions are d e v e l o p e d a t t h e cathode.
b e c a u s e t he y m a i n t a i n t he pH in t h e electrolyte. To c r e a t e the
c orre c t a l u m i n i u m c o m p l e x e s , t h e pH m u s t be close to 7.
T h e r e a re m a n y m e c h a n i s m s w h i c h a re a t w o r k in t h e
electrolytic cell. These i n c l u d e a n e l e c t r o p h o r e s i s m e c h a n i s m ,
w hi c h m a k e s t he negatively c h a r g e d oil p a r t i c l e s a t t r a c t e d to th e
anode. This r e s u l t s in a f a s t e r flocculation t h a n w oul d be t h e cas e
w i t h c o n v e n t i o n a l flocculation or fl ot a t i on me t hods . I'll

Gas b u b b l e f o r m a t i o n
The ga s b u b b l e s w h i c h a re c r e a t e d by e l e c t r o l y s i s have an
i m p o r t a n t function in t h e s e p a r a t i o n process. Reay a n d Ratcliff
found t h a t t h e r a t e of f l o t a t i o n of polystsTene ~ a r t i c l e s is
d e p e n d e n t on t h e ga s bubble- a n d p a r t i c l e di a me t e r. [~2] The r ate
of fl ot a t i on a t a c o n s t a n t gas ra t e v a ri e s as d ~2 rt~c t"e a n d d.-i
~- This
O~oole *
m e a n s t h a t t he ra t e of fl ot a t i on is a t its h i g h e s t when t h e p a r t i c l e s
are as large as p o s s i b l e a nd w he n t h e gas b u b b l e s are as s m all as
possible. Collins a n d J a m e s o n found t h a t t he r a t e of flotation of
pol ys t yre ne l a t e x p a r t i c l e s w i t h a d i a m e t e r of 4 - 20 /zm v ar ied as
l~5ti, te. [121 They a l s o found t h a t t h e e x p o n e n t s h o w e d little
pe'r~dence on t h e c ha rge on t h e particle, b u t t h a t th e a c t u a l
r a t e of fl ot a t i on w a s s t r o n g l y influenced by t he p a r t i c l e charge,
w hi c h w a s va ri e d in t he 3 0 - - 6 0 mV range.
There is a specific ra t i o between t h e sizes of t h e p a r t i c l e s a n d
t h e b u b b l e s w he re t h e r e is a h i g h e r p r o b a b i l i t y (if d i r e c t collisions
be t w e e n gas b u b b l e s a nd particles. Ilzl A di re c t collision m a k e s t h e
gas b u b b l e a d s o r b ont o t h e particle, a n d m a n y di re ct collisions
d u r i n g a s h o r t t i m e give a high ra t e of flotation.
If a collision between a p a r t i c l e a n d a gas bubb le is to be
successful, t h e e ne rgy b a r r i e r r e p r e s e n t e d by t h e w a t e r film
be t w e e n t h e a c t u a l p a r t i c l e a n d t h e a c t u a l gas bubb le m u s t be
overcome. The collision velocity a nd t he p a r t i c l e m a s s d e t e r m i n e
t h e energy w hi c h is a v a i l a b l e d u r i n g t he collision; l a rg er p a r t i c l e s
h i t t h e gas b u b b l e s w i t h a g r e a t e r force t h a n s m a l l e r gas bubbles.
The relative velocities of a p a r t i c l e a n d a ga s b u b b l e i n c r e a s e w ith
t he difference in t h e i r d i m e n s i o n s . If t he ga s b u b b l e hi t s a relatively
s m a l l particle, t h e force from t h e collision will m a k e t h e p a r t i c l e
r e b o u n d from t h e ga s bubble. The h i g h e s t p r o b a b i l i t y for a
successful collision is w h e n t h e gas bubbl e collides p e r p e n d i c u l a r
to t he p a r t i c l e surface. There are d i s t r i b u t i o n curves a v a i l a b l e Ibr
a i r b u b b l e s a nd m i n e r a l p a r t i c l e d i a m e t e r to find the o p t i m u m
flotability. This is c o m m o n in t he m i n i n g industry. U:8
Collins a n d .lameson H2] r e p o r t e d t h a t t h e ga s b u b b l e (:ollection
Eebruary 1995

F~llration & Separation

CTROFLOCCULATION
efficiency for bubbles less t h a n
described by

100 ]~m in diameter can be

(dP~"~i~z~N
Ec =

(4)

\ dbubbb--/

1.90 when Pparticl~./pfluid = 1.0, and N - 2.05 when

P~,a,-ti,:t,~/Pfl~i,t = 2.5. This a s s u m e s t h a t the s t r e a m around the

where N -

sphere follows Stokes' Law for a flow a r o u n d a rigid sphere; that

electrical interactions between bubbles and particles do not have
any effect on the particle trajectory or on E(., and t h a t bubble
motions are not affected by the presence of the particles, p2]

T h e size of t h e g a s b u b b l e s
The following c o n d i t i o n s affect t h e
diameter :[~4]
[]
[: J
~:]
{~]
E]

gas b u b b l e

departure

Gas bubble contact angle.

Cathode surface morphology.
Current density.
Polarisation potential.
Gas bubble charge.

Parameters which are fixed or which are impractical to adjust in

order to obtain fine-sized gas bubbles are pH, temperature, reagent
(:,mcentration and the electrode material.
Khosla et al. Ua] and Glembotskiy et al. H51 have reported t h a t
The gas bubble size decreases with increasing current density.
Glembotskiy eta/. H5] have also found t h a t the hydrogen gas bubble
size increases with increasing temperature, and t h a t the smallest
gas bubbles were formed at pH 7. Khosla e t a / . U4I have also
successfully used pulsed electrolysis to generate very small gas
bubbles; with a pulse cycle time varied in the range of 30 ms and
the current density varied from 2 to 0.5 A / m 2, they observed an
mcreasin
n u m b e r of s m a l l gas b u b b l e s ( < 1 0 - - 1 5
#m).
()thers(~,,~Zl have reported gas bubble diameters of 20 #m during
,qectroflotation with a constant current density.

Gas b u b b l e f o r m a t i o n on t h e c a t h o d e
]'Irate are three basic steps in tbe development of gas bubbles:
mlcleation, growth and detachment. Nucleation occur in energyfiwourable places like pits and scratches. These places have a
higher voltage t h a n the rest of the cathode surface (see Reference
t 6, p. 305). Khosla et al.[14J reported that with pulsed electrolysis
I he energy-favourable places are less i m p o r t a n t as nucleation sites,
and that nucleation is more uniform over the cathode surface.
Growth is driven by expansion caused by a high internal
pressure and t r a n s p o r t of dissolved gas t h r o u g h the gas/liquid
interface because of s u p e r s a t m ~ t i o n of gas in the electrolyte. Hal
Another m e c h a n i s m which make gas bubbles grow is coalescence.
Fhis occurs when two gas bubbles touch, and coalesce into a single
Ras bubble. Sides (Reference 16, p. 309) described a m e c h a n i s m
called radial specific coalescence, and obsel~ced t h a t smaller gas
bubbles moved radially t o w a r d s a larger gas bubble and coalesced.
Another mechanism which make two gas bubbles coalesce is

Waste Water

when one gas bubble rolls across the.cathode surface, and coalesces
with every gas bubble which comes into its path. This gas bubble
will often grow larger t h a n necessary before it detaches. Sides (Ref.
16, p. 312) reported t h a t w h e n the electrode was tilted a few
degrees from the horizontal, the bubbles coalesced and made a
large front of gas bubbles, which 'scavenged' o t h e r bubbles in its
path. This is unfavourable for the rate of flotation, because gas
bubbles with smaller diameters are more effective t h a n gas bubbles
with larger diameters.
The third step is detachment. Its occurence is dependent on the
bubble contact angle and the size of the gas bubble. Pulsating
electrolysis gives the gas bubbles a shock, which makes the gas
bubbles detach earlier t h a n they would w i t h o u t the pulses. A
surface-active s u b s t a n c e in the electrolyte will reduce the surface
tension between the electrolyte, the surface of the cathode and the
gas bubbles, and make the gas bubbles detach sooner. Venczel (Ref.
16, p. 316) added gelatine, glycerine and beta-naphthochinolin to
the electrolyte; in m o s t cases the bubble diameter decreased. The
reason suggested is t h a t the surface-active substance results in
increased wettability of the electrode.
The 'Purifier' reported here has been tested with s o a p in the
electrolyte. This test gave a higher degree of separation with oil-inw a t e r emulsions. The d i s a d v a n t a g e is t h a t a surf'ace-active
s u b s t a n c e works as an emulsifier and stabilises the oil emulsion,
b u t it is probably possible to find surface-active s u b s t a n c e s which
increase the wettability of the cathode w i t h o u t working as an
emulsifier for pollutants in the water.

T h e 'Purifier', an e l e c t r o f l o c c u l a U o n unit d e s i g n e d b y
Jan Sundell
Before the wastewater enters the electrolytic cell, it is coarsely
filtered in a hydrocyclone. This removes the larger particles, and
improves the total degree of separation. It was mentioned earlier
that there is a problem with the anode, which will tend to scum. [2}
This problem is solved in the Purifier. J a n Sundell h a s designed and
p a t e n t e d a system which keeps the anode clean all of the time, and
makes the anode wear evenly.
In the electrolytic cell aluminium ions precipitate from the
anode and flocculate the u n w a n t e d particles like oil, m o s t kinds of
organic c o m p o u n d s and heavy metals. At the same time the
hydrogen gas bubbles which form at the cathode cause the
flocculated particles to float. The residence time of the wastewater
in the electrolytic cell is less t h a n 1 s, but this d e p e n d s on the flow
velocity of the water. The w a t e r flows into a sedimentation tank,
where the residence time is short, but d e p e n d s on the temperature,
the concentration of impurities etc.
This process forms both a sediment and a layer floating on the
surface, which are removed at regular intervals. The sediment is
drained regularly, and the surface layer is skimmed off. The sludge
is dewatered in a filter, and the removed water is recycled into the
electrolytic cell. The sedimentation tank is t a p p e d for clean water
at regular intervals.
If the wastewater conductivity is too low, it is necessary to add

'T"

Electrolytic
..... Cell
1

Sludge~
Water and
Salt

_I_........

__
:~ecycled

Figure 1. Flowsheet for

the Purifier.

Water

Pure water

......

Reverse

Osmosis
Hydro Cyclone
...... 7

ily Sludge
Filtration & Separation

February 1995

155

CTROFLOCCULATION
I
s o d i u m c h l o r i d e to i n c r e a s e t h e c o n d u c t i v i t y . If t h e r e c i p i e n t
c a n n o t a c c e p t s a l t w a t e r , it will be n e c e s s a r y to r e m o v e t h e salt.
T h i s is d o n e w i t h t h e u s e o f a r e v e r s e o s m o s i s unit. T h e u n i t
produces two streams, one with pure water and the other with a
m i x t u r e o f s a l t a n d w a t e r . T h e l a t t e r s t r e a m is r e c y c l e d b a c k t o t h e
e l e c t r o l y t i c cell for r e u s e o f t h e salt.
The Purifier has achieved prominent results with the separatioH
of different kinds of pollution from water. Especially good results
h a v e b e e n a c h i e v e d in t h e s e p a r a t i o n o f oily e m u l s i o n s , a n d it ha.~
also a c h i e v e d a h i g h d e g r e e o f s e p a r a t i o n w i t h s e v e r a l k i n d s ni
o r g a n i c s u b s t a n c e s a n d h e a v y m e t a l s . T a b l e 1 g i v e s v a l u e s whiclp
w e r e a c h i e v e d d u r i n g t e s t i n g o f t h e P u r i f i e r ( t h e a n a l y s i s wa:~
p e r f o r m e d by t h e KM L a b o r a t o r y in K a r l s t a d ) .
T h e US c o m p a n y E n v i r o n o m i c s h a s also d e v e l o p e d a proces:~
which uses the electroflocculation principle, which has achieved
good results for s e p a r a t i o n of p o l y a r o m a t i c h y d r o c a r b o n s (PAHs)
oil, o r g a n i c c o m p o u n d s a n d h e a v y m e t a l s f r o m w a s t e w a t e r .

Acknowledgment
T h i s w o r k h a s b e e n f i n a n c e d by t h e L e t t e n F. S a u g s t a d s F u n d .

References

Figure 2. The Purifier unit, Including electrolytic cell,

sedimentation tank and process control system.

Table 1. Results from test rune with the Purifier.

Before the
Purifier, mg/I

After the
Purifier, mg/I

1. Oil in water

350

0.3

2. Atiphats in cooling water

Aromats in cooling water

260
62

2.4
0.6

3. Lead, Pb2+
Copper, Cu 2+
Zinc, Zn 2+

5.3
110
160

<0.05
1.2
0.22

Table 2. Results from Environomics Inc (1993).

Wastewater from
laundry

Before
separation, mg/I

After separation,
mg/I

3.4
5.7
3,4
3.4
3.4

0.079
0.240
< 0.33
< 0,33
< 0.33

Total oil and grease

Oil and grease

5500
4000

40
10

Phenol
TSS
Ethylbenzene
Toluene
Xylene

3,4
3500
21
23
168

0.052
22
< 0.007
0.014
0.051

Cd2+
Pb2+

25.6
400

<0.001
0.03

Naphtalene
2-bis ethylhexylphtatate
Pyrene
Fluoranthene
Chrysene

156

1 Weintraub, M.H., Gealer, R.L., Golovoy, ~ and Dziecioch, M.A.: 'Development ol

electrolytic treatment of oily waste water', En~ironme~r.tal Progress, Februar~
1983, 2(1), p. 32.
2 Fukui, Y. and Yuu, S.: 'Colle('tion of submieron particles in electro-flotation'
Chem. Eng. ~'ci., 1980, 35, pp. 1097- 1105.
3 Mallikarjuan, R. and Venkatachalam, S.: 'Elektroflotation
A review'
[nternatmnal Symposium nn Electrochemistry in Mineral & Metal Processing
(165th meeting of the Electrochemical Society), Cincinnati, Ohio, USA, May 1984:
pp. 233 -- 256.
4 Kaliniichuk, E.M., Vasilenko, l.]., Shchepanyuk, V.Yu., Sukhovcrkhova, N.A. and
Makarnv, I.A.: 'Treating refinery waste waters to remove emulsified oils by
electroeoagulation and electrofiotation', Int. Chem. Eng., July 1976, 16(3), p. 434.
5 Hosny, A.Y.: 'Electroflotation technique for removing petroleum oil wast(;',
Bull. Eleetrochem., January 1991, 7, p. 38.
6 Chamt)ers, D.B. and Cottrell, W.R.T.: 'Flotation: two fresh ways to treat
effluents', Chem. Eng., Augusl 1976, 83, p. 95.
7 Mork, P.C.: 'Overfiate og kolh)idk
jemi, 3rd edition' (]nstitutt for Indus
t r i e l l Kjemi, Norges T e k n i s k e
Hogskole, Nnrway, 1991.
8 Diggle, J.W. and Vijh, A_K.:'Oxides
and oxide films', in: Alwitt. R.S.: 'The
a l u m i n i u m w a t e r system, vol. 4'
Degree of
Example
(Marcel Dekker, New York, 1976),
Chap. 3, pp. 169 254
separation
9 Balmer, L.M and Foulds, A-W.:
'Electro fh)cculatiun/electrnflotation
99.9%
Car wash unit
fnr the removal ofoil from oil-in-water
emulsions', l~ltration & Separation,
99.1%
Ship
November/December 1986. 23(6), p.
366.
99.0%
10 ]logan, P. and Kuhn, A.T.: 'Die
>99%
Printing office
Electroflotation be] der Abwasserbe
98.9%
handlung', ObeFflache-Snrface, 1977,
18(10), p. 255.
99.9%
11 Hosny, A.Y.: 'Separation ()foil from
oil/water emulsions using an electroflotation cell with insoluble electrodes', F i l t r a t i o n & S e p a r a t i o n ,
September/October 1992, 29(5), pp.
419 423.
12 Collins, G.L. and Jameson, GJ.:
'Experiments on the flotation of fine
particles -- The influence of particle
size and charge', Chem. Eng. Sci.,
Degree of
Type of
1976, 31, pp. 985-991; Reay, D. and
s e p a r a t i o n compounds
Rateliff, G.A.: Canadian J. Chem.
Eng., 1975, 53, p. 481.
13 Klassen, \~I. and Mokrousov, V.A.:
97.7%
Polyaromatic
'An introduction to the theory, of
95.8%
hydrocarbons
flotation' (Butterworths, London,
> 91%
(PAHs)
I963).
> 91%
14 Khosla, N.K., Venkatachalam, S.
> 91%
and Somasundaran, P.: 'Pulsed electrogeneration of bubbles for electro
flotation', J. Applied Electrochem.,
99,3%
Oil fractions
1991, 21, p. 986.
98.8%
15 Glembotskiy, V.A~, Mamakov, A..~
and Sorokina, V.N.: 'The size of gas
98.5%
Organic
bubbles formed under electroflotation
99.4%
compounds
conditions', Electrochemistry in in
dustrial processing and biology,
> 99,97%
661.931, p. 66 (Scientific Information
99;94%
Consultants,
London).
99,97%
16 White, R.E., Bockris, J.O'M. and
Conway, B.E.: 'Modern aspects of
>99.996%
Heavy metals
electrochemistry' (Plenum Press, Lon99.993%
don, 1986), Chap. 6.

FeDruary 1995

Filtration & Separation