Coagulation & Flocculation
Coagulation & Flocculation
Coagulation & Flocculation
Flocculation
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one
the
Solutions
Colloidal dispersions
Suspensions
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following
states
are
Characteristics of Solutions,
Colloidal Dispersions and
Suspensions
System
Particle
Size
Separation
Method
Particle
Visibility
Particle
Movement
Solution
< 20
Membrane
Invisible
Kinetic
Colloidal
dispersion
20 - 2000
Ultrafiltration
Ultramicroscope
Brownian
Suspension
> 2000
Filtration
Microscope
Convective
1 = 10-4 m = 10-10 m
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organic materials
metal oxides
stable emulsions
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Coagulation
Coagulation is the process by which colloidal
particles and very fine solid suspensions
initially present in a wastewater are combined
into larger agglomerates that can be separated
via sedimentation, flocculation, filtration,
centrifugation or other separation methods
Coagulation is commonly achieved by adding
different types of chemicals (coagulants) to the
wastewater to promote destabilization of the
colloid dispersion and agglomeration of the
resulting individual colloidal particles
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Types of Colloids
Colloids are commonly classified as:
hydrophilic (e.g., proteins)
hydrophobic (e.g., clays, metal oxides)
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Hydrophilic Colloids
Hydrophilic colloids are typically formed by
large organic molecules that become hydrated
(solvated) when they are in the presence of
water
These molecules are thermodynamically stable
in their solvated form
The charge in such molecules originates from
the presence of ionizable groups on the
molecule that transform the molecule in a
"macro-ion" when placed in solution
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Hydrophobic Colloids
Hydrophobic colloids are made of small
colloidal particles having little or no affinity for
water (the solvent)
Their stability in due to the presence of a
charge which attracts other ionic species
present in water and results in the formation of
an electrically charged layer around the
colloidal particles
Colloidal dispersions are thermodynamically
unstable. If the charge layer is removed these
particles tend to agglomerate spontaneously
and can be removed from the wastewater
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- +
+
+
- + +
- +
+
Colloidal
- +
Particle
- + - +
- + +
+
+
+
Stern
Layer
Diffuse
Layer
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Zeta Potential
The zeta potential is defined as the electric
potential difference between the shear plane of
a colloidal particle and the bulk of the solution
The zeta potential is an indirect measure of the
electrical charge of the colloidal particle
The zeta potential can be experimentally
measured
(using
a
microscope)
by
determining the velocity of a particle moving
under an electric potential of known intensity
(Note: the actual potential between the surface
of the particle and the solution cannot be
measured experimentally)
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Shear Plane
Zeta
Potential
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4 v 4 EM
=
Vx
= 12EM
where:
= zeta potential in mV
EM = electrophoretic mobility in (m/s)/(V/cm)
Average zeta potential for wastewater colloids:
-16 to -22 mV (range: -12 to -40 mV)
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35
0
30
Residual Turbidity
Zeta Potential
25
-10
-20
Residual Turbidity
(Jackson turbidity units)
20
-30
15
-40
10
-50
0
0
100
200
300
400
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500
-60
600
10
Isoelectric Point
When the colloidal particles are in the
presence of enough counter ions they become
electrically neutral
This point is called the isoelectric point
The zeta potential at the isoelectric point is
zero
If the particles are not any more "shielded" by
the double layer they can interact with each
other
Hence, at the isoelectric point the particles
have the highest potential for agglomeration
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Coagulation as a Process of
Destabilization of Colloids
Coagulation of colloids occurs when a stable
colloid (because of the intrinsic stability of the
colloid dispersion) or a stabilized colloid
(because of the presence or a double layer) is
destabilized
Destabilization of colloids occurs when the
colloidal particles are brought close enough to
each other for agglomeration to occur
Several destabilization
possible
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mechanisms
are
Destabilization Mechanisms
Depending on the type of colloidal suspension
that should undergo coagulation different
destabilization mechanisms can be employed
such as:
Repression of the double layer
Neutralization of colloid charge by adsorption
of counter ions on the surface of the colloid
Bridging of colloidal particles via polymer
addition
Entrapment of colloidal particles by sweeping
floc
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z = 0. 33 10
I
where: z = thickness of layer, in cm
= dielectric constant for the solution, in C/(V cm)
I = ionic strength, in moles/L
2
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3.0 10 8
z
I
where z is in cm and I is in moles/L.
Example:
for I = 0.001 M
z 100
for I = 0.1 M
z 10
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Electrical Potential
Z2
Z1
Distance from Particle Surface
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Al2(SO4)14H2O (alum)
FeCl3
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Characteristics of Coagulants
The ability of a chemical additive to produce
coagulation is in general dependent on the:
electric charge of the ion or molecule used as
coagulant: the larger the charge the more
effective the coagulant will be;
size of the ion or molecule used as coagulant:
the larger the size of the molecule the more
effective the coagulant will be.
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Against Positive
Colloids
Against Negative
Colloids
NaCl
Na2SO4
Na3PO4
BaCl2
MgSO4
AlCl3
Al2(SO4)3 *
FeCl3
Fe2(SO4)3 *
1
30
1000
1
30
1
30
1
30
1
1
1
30
30
1000
>1000
1000
>1000
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Common Coagulants
The most common coagulants used in wastewater
treatment are:
Aluminum salts (alum)
Ferric and ferrous salts
Lime
Cationic polymers
Anionic and non-ionic polymers
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Formula
Mol.
Weight
Density
(kg/m3)
Alum
Al2(SO4)3
Al2(SO4)14H2O
Al2(SO4)18H2O
FeCl3
Fe2(SO4)3
Fe2(SO4)37H2O
Ca(OH)2
342.1
594.3
666.7
162.1
400
278
74.1
2710
Ferric chloride
Ferric sulfate
Ferrous sulfate
Lime
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2800
1899
3097
2200
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Alkalinity
level
Destabilization
mechanism
Al and Fe Addition
Strategy
High
Low
Charge
neutralization
Easy coagulation
High
High
Charge
neutralization
Low
High
Sweeping floc
High dose.
Easy coagulation
Low
Low
Ineffective
Increase alkalinity or
use other coagulant
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Lime as a Coagulant
Lime is a generic name used to identify several
combinations of calcium and oxygen, such as
Ca(OH)2 or CaO (quicklime).
Lime often
contains magnesium
In the presence of bicarbonate ion lime will
react to form a calcium carbonate precipitate
that can remove colloids through the sweeping
floc mechanism. The reaction involved is:
Ca(OH )2 + Ca(HCO3 )2 2 CaCO3 + 2 H 2O
If the wastewater is acidic the lime addition
will go first toward the neutralization of the
acid before colloid removal can take place
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Polyelectrolytes as Coagulants
Polyelectrolytes (also often referred to a
polymers in coagulation processes) are
synthetic or organic polymeric molecules having
ionizable groups or charged groups along their
chain
Polyelectrolytes can be classified according to
their origin as:
- natural, i.e., derived from starch products or
of biological origin (e.g., alginate from algae,
chitosan from the acidification of chitin in
shells)
- synthetic, i.e., synthetically polymerized from
monomers (e.g., polyamine, sulfonate, etc.)
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Polyelectrolytes as Coagulants
Polyelectrolytes are also classified according
to the charge that they have when they are in
solution as:
-
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Examples of Polyelectrolytes
Type
Functional
Group
Example
Cationic
Amine
Polyethyleneamine
hydrochloride
Quaternary
Polydiallyldimethylammonium
Polyalcohol
Polyvinylalcohol
Amide
Polyacrylamide
Carboxylic
Polymethacrylic acid
Sulfonic
Polyvinylsulfonate
Nonionic
Anionic
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Examples of Coagulant
Polyelectrolytes
Cationic
H
CH2
CH2 N
Anionic
Nonionic
CH2
CH
C O
NH2
Cl
n
Polyethyleninine
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R
CH2
CH
C O
O
n
Polyacrilamide
Poly(meth)acrilic acid
Polyelectrolytes as Coagulants
Cationic polyelectrolytes are typically used to
coagulate colloids that are negatively charged
(the most common type)
The mechanisms involved in the colloid
destabilization by cationic polyelectrolytes are:
charge neutralization and bridging of colloidal
particles
Nonionic and anionic polyelectrolytes can also
be used to destabilize negative colloids. In
this case the destabilization mechanism is not
too well elucidated but is believed to be due to
bridging
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Dosage (ppm)
pH
Alum
75 - 250
4.5 - 7.0
FeCl3
35 - 150
4.5 - 7.0
FeSO47H2O
70 - 200
4.0 - 7.0
Lime
150 - 500
9.0 - 11.0
Cationic Electrolytes
2-5
---
0.25 - 1.0
---
Coagulant Aids
Despite their names coagulant aids are
additives that can be added to a destabilized
colloidal suspension to promote the growth of
large, rapid-settling floc which can then
flocculate
Typical coagulant aids are:
-
Activated silica
Polyelectrolytes
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jar test
zeta potential
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Jar Test
The jar test is the most common laboratory
coagulation test and consists of:
placing a sample of the wastewater in a jar:
rapidly adding the coagulant and intensely
mixing the sample for a short time
(coagulation/destabilization phase);
allowing the floc to form under gentle mixing
conditions (flocculation phase)
allowing the floc to sediment in the quiescent
sample (settling)
comparing the turbidity of the sample with the
initial turbidity
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After Droste, Theory and Practice of Water and Wastewater Treatment, 1997, p. 388.
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Pollutant
Residual Concentration
Pollutant
Residual Concentration
pH
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Coagulant Dosage
Mechanisms of Flocculation
Perikinetic flocculation
This type of flocculation is generated by the
Brownian motion associated with destabilized
small colloidal particles. The Brownian motion
contributes to transport the particles close
enough for agglomeration to occur
Orthokinetic flocculation
This type of flocculation mechanism is based on
the generation of velocity gradients within the
wastewater to promote particle interaction. In
this case a mild agitation promotes the
aggregation of the particles and hence
flocculation
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Pave
=
V
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Gxy
dv x
=
dy
y
x
vx=0
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dv x
xy =
dy
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where:
= power dissipation per unit fluid volume
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P
V
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C
D
T
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Submerged Impellers
Many different types of impellers exist.
Impellers are classified on the basis of:
shape
dimensions
type of flow pattern generated
flow intensity
power consumption under aerated and nonaerated conditions
their ability to disperse a gas effectively.
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Pitched-
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Baffle
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Power Number
The power number, Po (or Ne or Np) is a nondimensional number used to calculate the
power consumption of an impeller.
In general, the power number is a function of
the type of impeller, type of agitation system
(e.g., tank, baffles), dynamic agitation regimes
(e.g., turbulent flow, laminar flow), geometric
dimensions of impeller and tank, location of
the impeller, and the presence of other
impellers. In other words, Po is a function of
any variable affecting the agitation flow.
Po is typically determined experimentally.
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N 2D
Froude Number = Fr =
(important only in
g
unbaffled vessels)
Geometric Ratios, such as T ; H ; C ; w
D D D T
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P
Po = Ne =
,
, , , , ,impeller type
3
5 = f
g D D D T
N D
P
Po = Ne =
= f
, , , , ,impeller type
N3 D5
D D D T
Power Number
100
10
Laminar
Turbulent
Transitional
1
1
10
100
1000
Reynolds Number
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10000
100000
Transitional Regime:
Po = Ne = f (Re)
Turbulent Regime:
Po = Ne = Constant
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Po or Ne
9.8
8.5
Gate
5.5
5.0
4.0
1.3
Prochem
1.0
0.75
MIG Impeller
0.65
Lightnin A310
0.45
Propeller
0.35
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Plan View
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Side View
b
Shaft
ri
ro
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W = p dV
Vi
where:
p = pressure in the gas bubble
V = bubble volume
o subscript: at the top of the tank
i subscript: at the bottom of tank
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pV = po Vo = pi Vi = nRT
Then:
Vo
W =
Vi
po
dp
pi
p dV = ( po Vo ) = ( po Vo )ln
p
po
pi
t
t
po
po
po
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p = L g h
where h is the height of the column of liquid, and
L is the density of the liquid.
Since 1 atm = 101,325 Pascals the height of a
column of water that produces a hydrostatic
pressure of 1 atm is:
101325
,
Pa
h=
= 10.3 m
3
2
1000 kg / m 9.81m / s
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p
h (in m)
P = po Qo ln1 +
= po Qo ln1 +
10.3
po
h (in ft)
= po Qo ln1 +
33.8
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P = g Q hL
where:
= liquid density
g = acceleration of gravity
hL = headloss in the device
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20
30
40
>40
1000
900
790
700
20,000
27,000
31,600
28,000
G (1/s)
Gt
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Horizontal-shaft
paddle
Baffled channel
James M. Montgomery Consulting Engineering, Inc., Water Treatment Principles and Design, 1985, p. 516.
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Horizontal-shaft
Paddle
Baffled channel
James M. Montgomery Consulting Engineering, Inc., Water Treatment Principles and Design, 1985, p. 516.
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Examples of Coagulation-Flocculation
Processes for Industrial Wastewaters
Wastewater
Source
Contaminant
Type of
Coagulant
Dosage
(ppm)
Petroleum
refinery
Oil
Alum
25-75
Petroleum
refinery
Foam
Polyamine
1-3
Steel mill
Oil
Anionic
1.5-2
Steel mill
Suspended solids
Anionic
0.3
Paper mill
Suspended solids
Weak cationic
2-5
Suspended solid
removal (%)
Without
With
Without
With
Without
With
5-10
70-90
40-70
60-75
25-40
40-50
Trickling
filters
10-20
80-95
70-92
85-95
80-90
85-95
Activated
Sludge
10-20
80-95
85-95
85-95
85-95
85-95
Primary
treatment
Secondary
treatment
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