ENE-302

Water Treatment

Chapter 3

Coagulation-Flocculation

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 FLOCCULATION
t=0 t=t
I am Bigger So
Faster

g
VS = (  S  L dp
- ) 2
VS  dp
2
18 
Nature of Colloids

Stages of Flocculation NTU Jar Test

Rapid Mixing
Flocculation C
 Coagulation-Flocculation
Coagulant
(Alum or Iron)
Coagulant aid
Alkalinity (polymer)

RAW WATER to FILTER

Settling tank

Colloids Destabilization Floc generation

COAGULATION FLOCCULATION SEDIMENTATION

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 Coagulation
Principle
When certain chemicals are added to raw water containing slowly
settling/non-settleable particles,
the smaller particles begin to form larger or heavier floc
can be removed by sedimentation.

Objective
Through elimination of SS, moderate reduction of organic
pollution from wastewater
I am Coagulants
We are bigger
 settling
faster

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 Different Principles in SS Removal
Sedimentation:
The direct use of gravity in the form of straight forward
sedimentation - where the determining factors are:
Particle size g
VS   S   L d 2

Specific weight (S/L) 18 

Relationship between Particle Size and Settling Time

Particle diameter Particle Type Settling Time
mm (through 1 m)
10 mm Gravel 1 second
1.0 mm Sand 10 seconds
0.1 (100 µm) Fine Sand 2 minutes
0.01 (10 µm) Clay 2 hours
0.001 (1 µm) Bacteria 8 days
0.0001 (0.1 µm) Colloidal Particles 2 years
0.00001 (0.01 µm) Colloidal Particles 20 years
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 Different Principles in SS Removal

Flotation:
Introduction of air bubbles, SS are attached to the bubble
surface and collected at the top surface of the flotation unit
Hydrocyclones and Centrifuges:
When the conventional sedimentation is accelerated
with the aid of centrifugal force (g)  not an
economic solution

Filtration and Screen:

Efficient only when particle size is >1 m
Have to reduce the load of Suspended Solids - to avoid
frequent filter bed clogging

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Colloids
Particle diameter () < 1 m  cannot be removed from
suspension by ordinary physical separation processes;
Very slow settling characteristics of colloids (Brownian
motion hinders their settlement under the effect of gravity);
Contribute large parts of pollution and specific cause of
turbidity (higher ratio of surface area to mass)
Surface properties ( potential and electrical charges)
becomes more important than sedimentation under gravity

Surface area Mass

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Colloids

Relationship between the Particle Size & Surface Area

Particle () Number of Surface

(µm) Particles Area:mass
cm2/g
250 µm 1 0.00375 cm2
1 µm (250)3 1.00 cm2
-3
1 x 10 µm (250 x 1000)3 1000 cm2

 Surface area   Surface area 

   
 mass colloids  mass  particle

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Surface Properties of Colloids

Adsorption: Tendency to concentrate substance from the

surrounding (higher surface area/mass ratio).
Application in water treatment: activated carbon is used as an
adsorbent to remove taste and odor problems (due to unwanted
colloidal matters)

Electrokinetic Properties: Tendency to develop charge in relation to

the surrounding medium.
Colloidal particles are normally charged
Electrical charge = f (colloidal material & surrounding medium)

4 q
 Zeta Potential   
D
q = Charge on the particle (or the charge difference between the particle
and the body of the solution)
 = Thickness of the layer around the particle.
D = Dielectric constant of the medium.
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Surface Properties of Colloids
Electrophoreses:
If electrodes from a DC source are placed in colloidal suspension,
the particles migrate towards the pole of the opposite charge at a
rate proportional to the potential gradient set up in the solution.
UEP  E where UEP = Electrophothetic Mobility

- +
- - +
+
- +

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 Zeta Potential

Zeta Potential:
A measure of both the charge on a colloidal particle & the distance
into the solution to which the effects of the charge extends
Diffuse layer of counter
ions (moving part)
Electro-negative
particle

E
Rigid layer attached to
Zeta Potential ()
particle


Electrical Relations at Surface of the Colloids

One part of the double layer is fixed to the walls of the particle
The other is made of diffuse as cloud of ions.
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Zeta Potential
 (Zeta potential) = The difference in the potential between the
surface separating fixed and moving parts of the liquid.
 = f(the double layer thickness)
 is measured using a zetameter, when the mobility of colloidal
particles across a cell, as viewed through a microscope.
Colloidal silica minerals and most proteins are negatively charged
Hydrous oxides of iron and aluminum are usually positively charged

Hydrous oxides of
Fe, Al
Colloidal Silica minerals,
proteins
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Properties of Colloids

Colloidal particles are normally charged with respect to the

surrounding medium
Hydrophobic: (e.g. Clays and Metal Oxides) WATER HATING
Colloids possess no affinity for the liquid medium.
They are readily susceptible to coagulation.
Majority of inorganic colloids.

Hydrophilic: (Proteins) WATER LOVING

Exhibit a marked affinity for water.
Adsorb water and retards flocculation and frequently
needs special treatment to achieve effective coagulation.
Majority of organic colloids.

When colloidal particles come into contact, they join to form

large particles, flocculates and precipitates 13
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Coagulation/Destabilization

Reduction of surface potential by charge

neutralization.
Enmeshment of colloids in a precipitate.
Adsorption and Interparticle bridging.

Charge Neutralization:
Adsorption of a species carrying a charge opposite to that
of colloids.
Reduction of surface potential & destabilization of colloids.
Increase in dosage of coagulant with increase in
concentration of colloids.
Overdose of coagulant cause restabilization.
Optimum coagulation when  0 mV.
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Bridging Mechanisms

Reaction 1: Initial adsorption at the optimum polymer dosage

Polymer Particle Destabilized particle

Polymer molecule will become attached to a colloidal

particle.
 columbic attraction if the polymer and particle are of
opposite charge

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Bridging Mechanisms

Reaction 2: Floc formation

Flocculation

Perkinetic or
Orthokinetic
Destabilized particle Floc particle

The tail of the absorbed polymer will extend out into the
bulk of solution
and can become attached to vacant sites on the surface of
another particle. This bridge  floc formation.

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Bridging Mechanisms

Reaction 3: Secondary adsorption of Polymer

No contact with vacant sites

on another particle

Destabilized particle Restabilized particle

If the extended segment fails to contact another particle it

may fold back and attach to other side on the original
surface  restabilizing the particle.

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Bridging Mechanisms

Reaction 4: Initial adsorption excess polymer dosage

Particle
Stable particle
(no vacant site)
Excess Polymers

If excessive polymer is added, the segment may saturate

the surface of colloidal particle  no sites are available
for formation of polymer bridges.
This is can restabilize the particles and may or may not
be accomplished by charge reversal.

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Bridging Mechanisms

Reaction 5: Rupture of floc

Intense or
prolonged agitation

Floc particle

Rupture of particles if mixing is too high

For whole process (5 reactions):

Major mechanism: Adsorption & inter-particle bridgings
Minor mechanism: Charge neutralization
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Type of Coagulants

The most frequently coagulants: Fe(III) and Al(III)

Aluminum sulfate (Alum) Al2(SO4)3.14H2O M.W = 554.2
Ferric chloride FeCl3 M.W = 162.2
Mainly for economical reasons
Highly pH dependent

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Polyelectrolytes
(sub-units contain ionizable -COOH, -OH, -NH2+ and R1NR2+)

Organic Polymers:
Long-chained macromolecules either occurring naturally or
obtained by linking the synthetic monomers.
Natural polymers are relatively inefficient.
But synthetic polymers are highly efficient

Synthetic Polymers:
Can often carry electrical charges or groups which can be
used for ionization (MW of several millions)
But often there is regulation regarding usage of synthetic
polymers in water treatment plants (Residual amount of
polymers).

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Properties of Polymers

Soluble in water
Affected by electrostatic forces between their charges
Non ionic polymers : (mainly of polyacrylamids)
Anionic : polyelectrolytes (- Ve)
Cationic: polyelectrolytes (+Ve)
MW : 106 - 108
 often charged polyelectrolytes are used as coagulants :
(only cationic polymers)

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Flocculation of bacteria

Dispersed microorganisms
A B C D
1000
as COD, mg/L
800 A: No flocculation
B: Slow flocculation
600 COD of
supernatant after C: Rapid flocculation
1h of settling
400 D: Redispersion
Soluble COD
200
1 2 5 10 20 100 500
Purifloc 602, mg/L
Flocculation of dispersed microorganisms by a Cation polyelectrolyte

With increasing amounts of added polyelectrolyte, a greater

fraction of microbial surface becomes covered until flocculation
becomes optimal.
Beyond this point there is a mutual repulsion and redispersion of
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Determination of coagulant Dosage
Using a Jartest :
Take known volume of the sample
Add known increment of Coagulant
Rapid mixing for 3 min. slow mixing for 12 min.
Determine ZP and/or turbidity

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Coagulant Aids/Flocculants

Flocs produced during a coagulation process should :

Settle rapidly
Resistance to destruction by shearing forces

Low concentration of colloids (low turbidity, high color):

needs high concentration of coagulant
sweeps floc coagulation

Coagulant aids (flocculants) are used to increase the floc

properties  creating strong and fast settling flocs, e.g. clays,
activated silica and polymers.
Bentonite clays are frequently used as coagulant for low turbid
water  lead to decrease in amount of coagulant and increase the
nature of the floc produced (fast settling flocs)

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 Coagulation (Charge Neutralization)
Effective
radius
+
– – –
–
– – –
+ +
– + + +
– + +– –
– –
+ Stable
–
– – + + +
Colloid
+ –
– +– + –– +

+ +
+
– –

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Coagulation Process Equipment
Coagulation in two stages:
Destabilization of colloids
Particle transportation to promote collision of colloids.

Objectives
Neutralization/destabilization of colloids.
The reagent has to be diffused as rapidly/quickly as possible
throughout the volumes of the water
The volume of reagent solution added is very small in comparison
with the main flow of the water.

The Essential Features of a Good Mixing Device are :

Adequate turbulence (by mixing flow direction).
Adequate backmixing (by mixing in the direction of the flow).
Rapid dispersion of chemicals.

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Static Mixers
Lack of moving parts (easy for O & M point of view)
Devices (screens, diaphragm) installed inside the pipes, which
causes enough turbulence to diffuse coagulant instantly.

Coagulant Roller: Zone of high turbulence,

but of only a low flow-through

Inlet
Outlet

Only low to moderate turbulence

in the main flow zone

Hydraulic jump do not provide efficient mixing

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 Static Mixers

Coagulant

From the plain jet, turbulence & energy

Inlet dissipation occur a large volume, with
little back mixing

Coagulant

Suitably placed baffles can intensify

energy disspation with some backmixing
Inlet
 improving mixing efficiency

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 Static Mixers
Disadvantages:
 Create high headloss
 Very inefficient when the flow through the pipe decreases
 Very low backmixing
Coagulant Static mixing element placed
lengthwise in a pipe

Inlet Outlet

Coagulant
Coagulant

Inlet

Inlet

Rotary or Slide valve Baffle 30

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Pneumatic Mixers
Compressed air is used as a mixing device
Introduced through submerged diffusers and causes turbulence
as it rises to the surface
Degree of turbulence/mixing is controlled by placement and type
of diffusers and by the applied pressures
Coagulant
Air

imlet

Air diffuser
Outlet

Problems:
Often the flocs can get attached to the tiny air bubbles  can upset
the subsequent sedimentation processes (because bulk density of a
floc particle containing air could  than the density of water)
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 Mechanical Mixers
Turbulence is induced through high speed rotating
impellers such as propellers, turbines and paddles
Energy intensive process  high O & M
Batch/Continuous.
Contact Time  1 - 2 minutes/30 - 60 seconds
Mean velocity gradient G = 100 to 1000 s-1

Camp Number = G x t

t = Residence time (s)

G = Parameter which evaluates the energy input necessary for
flocculation
dv
G 
dy
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 Flocculation
A slow stirring process that causes gathering together of
small coagulated particles into larger, settleable particles.

Flocculation theory
Coagulation: Theory of destabilization.
Flocculation: Theory of contacts between these
destabilized colloids

The three mechanisms of particle contacts:

1) Contacts by thermal motion: Brownian motion/diffusion
(upto  = 1m) Perikinetic flocculation
2) Contacts resulting from bulk fluid motion (e.g. transport
induced by stirring)  Orthokinetic flocculation
3) Contacts resulting from settling of the particles

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 Perikinetic Flocculation
Random motion of particles/colloids observed
The rate of change in the total concentration of particles
with time due to Perikinetic flocculation (JPK)

dN o  4 . .k .T
J PK   (N o )2
dt 3 .
No = total concentration of particles in suspension at time t
 = Collision efficiency factor (fraction of collision that produce aggregate)
k = Boltzman's Constant (1.38 x 10-16 erg/degree)
T = Absolute temperature (°K)
 = Fluid viscosity (kg/m.sec.)

The rate of Perikinetic flocculation is independent of particle size.

JPK is directly proportional to the concentration of colloids (is
more rapid in concentrated suspension than in dilute one)

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 Orthokinetic Flocculation
3
dN o  2 . .G .d
J OK   (N o ) 2
dt 3
d = Diameter of the colloids  JOK is function of particle diameter

J OK  .G .d 3

J PK 2 .K .T

For very small particles: the perikinetic flocculation dominates.

Ex: a colloid of 0.1 m needs a G value of 10,000 s-1 to have JOK =
JPK. But in practice such G is impossible to achieve.
If colloids  1.0 m and G = 10 s-1 , JOK = JPK.
The particles must aggregate to a size of approximately 1.0 m by
Brownian motion (perikinetic flocculation)
But once reaching this size, stirring must be provide to promote
further aggregation (orthokinetic flocculation).

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 Flocculation
Value of G and t:
The optimum value of G and t depends on:
Chemical composition of the water
Nature and concentration of colloids
G (s-1)
The optimum G tends to decrease with
Floc break
increase in turbidity.
Camp Number = G.t (dimensions unit)
Excess G  Floc Rupture Optimum
Excess t  Floc Erosion

Tapered Flocculation: t (s)

Ideal flocculation process should be:

1. Rapid initial flocculation with moderately high G
2. With decreasing G, providing floc growth without disruption.
Tapered flocculation: G  Progressively decreased with increased
size of flocs.
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 Flocculation Equipment

Types of flocculators:
Hydraulic: - baffled channels
Mechanical: - paddles and reel
- turbine
- propeller
G = 20 - 50s-1, t = 30 - 60 minutes

Baffled Channels:
Prior to 1920, only baffled channels were used for flocculation.
Simple in design, construction and O & M (no moving parts).
G is intensified by inducing changes in the flow direction.

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 Baffle Channel Flocculators
Shorter baffles
with wider spacing

Plant of side-to-side baffle channel flocculator

Increasing depth-decreasing velocity

Longitudinal section of under-and-over baffled channel flocculator

Vertical slots or
posts as baffles

Plan of channel flocculator with posts 38

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 Flocculation Basins
Shape is determined practically by the flocculator selected
Horizontal flocculators rectangular in shape while for
vertical flocculators nearly square
Depth of the basin is same like the sedimentation basin
Flocculation is best achieved by compartmentalized basin.
Compartments are to prevent short circuiting
Turbulence is reduced by succeeding compartments
(tapered flocculation)

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 Flocculators

PADDLE TURBINE PROPELLER

HORIZONTAL PADDLE WHEEL 40

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 Typical Flocculation Basin

Inlet

to sedimentation
tank

v = 75 rpm v = 50 rpm v = 25 rpm

Inlet

to sedimentation
tank
v = 75 rpm v = 50 rpm v = 25 rpm
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 Velocity Gradient
Measure of mean velocity gradient in the fluid:
P
G 
 .V
G = mean velocity gradient (s-1)
P = power requirement (W)
 = dynamic viscosity (NS/m2)
V = flocculator volume (m3)

Range of Values
Process
Detention Time G (s-1)
Mixing
Typical rapid mixing operations in ww treatment 5 - 20 s 250 - 1,500
Rapid mixing in contact filtration process <1 - 5 s 1,500 - 7,500
Flocculation
Typical flocculation process used in ww treatment 10 - 30 min 20 - 80
Flocculation in direct filtration process 2 - 10 min 20 - 100
Flocculation in contact filtration process 2 - 5 min 30 - 150
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 Power Requirement for Mixing
Propeller and Turbine Mixers:
Laminar (NR<10): P  k . .n 2 .D 3 10 < NR <10,000:
D 2 .n . 
Turbulent (NR>10,000): P  k . .n .D
3 5
NR 

NR = Reynolds Number  = mass density of the fluid (kg/m3)
P = power requirement (W) D = diameter of impeller (m)
k = constant n = revolution per second (rev/s)
 = dynamic viscosity (N.S/m2)
Impeller (k value) Laminar range Turbulent
range
Propeller, square pitch 3 blades 41 0.32
Propeller, pitch of two, 3 blades 43.5 1
Turbine, 6 flat blades 71 6.3
Turbine, 6 curved blades 70 4.8
Fan turbine, 6 blades 70 1.65
Turbine, 6 arrowhead blades 71 4
Flat paddle, 6 blades 36.5 1.7
Shrouded turbine, 2 curved blades 97.5 1.08
Shrouded turbine with stator (no baffles) 172.5 1.12

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 Power Requirement for Mixing
Paddle Mixers:
Recommended paddle tip speed : 0.6 - 0.9 m/s
This speed is sufficient to create a turbulence without
breaking the floc
Design equations of flocculation systems:
C D .A .  .v P2
FD 
2
FD = drag force (N)
CD = coefficient for drag flocculator paddles
A = area of the paddles (m2)
vP = relative velocity of paddles in fluid (m/s)
usually about 0.7 to 0.8 of the paddle-
tip speed

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 Power Requirement for Mixing
Static Mixers:
P   .Q .h
P = power dissipated (kW)
 = specific weight of water (kN/m3)
Q= flowrate (m3/s)
h = headloss dissipated as liquid passes through device (m)

Pneumatic Mixers:
Pc
P  Pa .V a . ln
Pa
P = power dissipated (kW)
pa = atmospheric pressure
Va = volume of air at atmospheric pressure (m3/s)
pc = air pressure at the point of discharge (kN/m2)
Assume that the work done when the volume of air released under
compressed conditions expands isothermally
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 Coagulation & Flocculation
Mainly in water treatment plants
Rarely used in wastewater treatment plants
Because:
Most advanced WWTP  Biological Systems  Not physico-
chemical
Biological systems do not need coagulation
Chemicals could react with wastewater  Could destroy
certain micro-organisms which are helpful in sludge digestion
High cost of chemicals - Bigger sedimentation tanks
Higher quantity of sludge
Need for skilled operators
Industry:
Chemicals/Electroplating
Suitable for large seasonal variations
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 Coagulation & Flocculation
PADDLE MIXER WITH HORIZONTAL SHAFT

Longitudinal section Cross-section of channel

PADDLE MIXER WITH

VERTICAL SHAFT

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 Flocculators

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 Coagulation Sedimentation
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