CV6501

Water Treatment & Process Design

(Part I)
Dr. Katherine Dongqing Zhang

School of Civil and Environmental Engineering

Nanyang Technological University

dqzhang@ntu.edu.sg
Coagulation and Flocculation

Today’s Lecture
Flocculation and its applications in water treatment

Typical layout of a water treatment plant

TABLE OF CONTENTS
1. Particles in ambient waters;
2. Stability of particle in water;
3. Coagulation theory;
4. Coagulation of dissolved constituents;
5. Coagulation practice;
6. Flocculation theory;
7. Flocculation practice.
3.1 PARTICULATE IN AMBIENT WATERS
PARTICULATE CONSTITUENTS
 Suspended solids: settleable and nonsettleable;
 Inorganic particulate
 Organic particulate
 Colloidal solids:
 Fine inorganic/organic particulates that do not settle
 Combined effect is often seen as color and turbidity
 Dissolved solids:
 Dissolved inorganic/organic constituents;
 Natural organic matter (NOM)
Size:
􀂃 Molecules: < 0.001 μm
􀂃 Colloids: 0.001 to 1 μm
􀂃 Bacteria: 1 μm
􀂃 Algae: 1-50 μm
􀂃 Protozoa: 5-100 μm
􀂃 Suspended solids: 0.5 to 1000 μm
􀂃 􀂃
Measure of particulate concentration in water:
􀂃 Turbidity: NTU (Nephelometric Turbidity Unit)
􀂃 Total/dissolved suspended solids (TSS/TDS): mg/L
Total/dissolved organic carbon (TOC/DOC): mg/L
Typical colloidal characteristics

• Size range: 10-3- 1 micron. (somewhere in the range

between a molecule and bacteria in size).

• 50 – 70 % of the organic matter in domestic

wastewater is composed of colloidal matter.

• In water treatment, color, turbidity, viruses, bacteria,

algae and organic matter are primarily either in the
colloidal form or behave as colloids.
 Why coagulation and flocculation is needed
Particle diameter Type Settling velocity
mm

Gravity settling
10 Pebble 0.73 m/s
1 Course sand 0.23 m/s
0.1 Fine sand 0.6 m/min
0.01 Silt 8.6 m/d
0.0001 (10 micron) Large colloids 0.3 m/year
0.000001 (1 nano) Small colloids 3 m/million year
PARTICLES CLASSIFICATION
HYDROPHOBIC
 Have a well defined interface between the water
the solid phases;
 Low affinity for water molecules;
 Negatively charged;
 Physical/chemical origin (e.g. clays, metal oxides,
sulfides);
 Classified as thermodynamically unstable or
“irreversible”.
PARTICLES CLASSIFICATION
HYDROPHILIC
 Have a great affinity for the solvent;
 Possess a slight charge (negative), but
dispersion is stabilized by hydration;
 Biological in origin: e.g., gelatin, starch, proteins;
 Have polar or ionized surface functional group;
 Inorganic particulates (silica, hydrated metal
oxides i.e. iron and aluminum oxide etc.) and
organic particulates (humic acids, viruses,
bacterial, protozoa, algae etc.)
 React spontaneously to form colloids in water.
3.2 STABILITY OF PARTICLE IN WATER
ELECTRICAL DOUBLE LAYER (EDL)
ELECTRICAL DOUBLE LAYER (EDL)
 The negatively charged colloidal particles attract
counter-ions by electrostatic attraction.
 A dense fixed layer of cations/counter-ions (known
as Helmholtz layer or Stern Layer) is attracted to
the surface of colloidal particles.
 A loose/movable diffuse layer of ions, of both
electrical charges (but positively charged ions
predominate) is formed beyond the Helmoltz layer.
 The double layer: Helmoltz plus diffuse layer.
 EDL will make colloidal particle in suspension
(stabilized).
ZETA POTENTIAL
NATURAL FORCES OF PARTICLES

 Electrostatic repulsion force

 Attraction force
o Brownian Motion
Random movement of colloids; allows particles to
move sufficiently close for van der Waals force to
predominate over electrostatic repulsion.
o van der Waals Forces
Cause interaction between any two masses; depends
on the mass and distance of the two bodies.
STABILITY OF COLLOIDS

 Stability of particles depends on a balance

between
a) The electrostatic repulsion force
b) The attractive force known as the van der
Waals force
 The principal mechanism controlling stability
- electrostatic repulsion force
 Particle destabilization – repulsion force
between particles is neutralized or reduced
 Particle-particle interaction

A stable suspension of particles where forces of repulsion

exceed the forces of attraction
 Colloid Stability
 Colloids have a net negative surface charge
 Electrostatic repulsion force prevents them from agglomeration
 Brownian motion keeps the colloids in suspension
 Impossible to remove colloids by gravity
settling

Colloid Destabilization
 Colloids can be destabilized by charge neutralization:
 Positively charged ions (Na+, Mg2+, Al3+, Fe3+ etc.) neutralize the
colloidal negative charges and thus destabilize them.
 With destabilization, colloids aggregate in size and start to settle
3.3 COAGULATION THEORY
 Coagulation is the destabilization of colloids by
addition of chemicals (e.g., alum - (Al2SO4)3.nH2O,
where n=14, 16, or 18) that reduce the negative
charges (the chemicals are known as coagulants,
usually higher valence cationic salt (Al3+, Fe3+ etc.));
 Destabilization of colloids is aimed to reduce zeta
potential or suppression of double layer by counter-
ions of coagulant;
 Rapid mixing is required to disperse the coagulant
throughout the liquid;
Mechanisms of Destabilization

 Double layer compression

 Charge neutralisation
 Enmeshment or sweep-floc coagulation
 Inter-particle bridging
Double-layer compression
 Addition of indifferent electrolyte increases the ionic
strength of solution - compressing the double layer.
 EDL thickness shrinks dramatically with increasing
ionic strength and valance:
Charge neutralisation
 Counter-ions adsorbed onto surface of colloidal
particles and neutralised the repulsive charges
Ionic strength and charge neutralization
Ionic strength and charge neutralization
Entrapment of colloidal by sweeping floc

 The metal salts (aluminum or ferric salts) used in

coagulation will react with alkalinity to form
hydroxides (Al(OH)3 or Fe(OH)3) which are
insoluble precipitates;
 As the hydroxide precipitate forms and
accumulates, smaller colloidal particles are
entrapped or enmeshed in the hydroxide flow
structures;
 Also known as sweep-floc coagulation;
 Large amounts of sludge are formed as a result.
Adsorption and inter-particle bridging

 Synthetic organic polymer is adsorbed onto the

colloidal and coagulant particles and grow into a
bigger and tougher floc particle, resulting in
particle agglomeration
3.4 COAGULATION PRACTICE

Characteristics of coagulants
 Electric charge of the cationic ion: the larger the
charge, the more effective the coagulant will be;
 Size of the cationic ion: the larger the size of
molecule, the more effective the coagulant will
be;
 Act as colloid destabilizers reducing the zeta
potential;
 Behave as sweep flocculent.
Reactions of coagulants in Water
REACTION OF ALUM IN THE PRESENCE OF CALCIUM
AND MAGNESIUM ALKALINITY
POLYALUMINUM CHLORIDE (PACL)

 High charge with moderate MW species, e.g.,

Al13O4(OH)27;
 Can form tougher and denser floc;
 Less temperature and pH sensitive;
 Allow full charge neutralization before sweep floc
formation;
 Lower dosage – less sludge;
ORGANIC POLYMER
 Polyelectrolytes: cation, anion and nonionic;
 May be used to replace alum or ferric iron as
primary coagulant;
 May be used in conjunction with a primary
coagulant;
 May function to bridge between other flocs and
settle with higher velocity;
 Less pH sensitive and sludge production;
 High price.
FACTORS AFFECTING COAGULATION
 pH
 Temperature
 Zeta potential
 Dosage
 Coagulant concentration
FACTORS AFFECTING COAGULATION
(ALKALINITY)
FACTORS AFFECTING COAGULATION
(pH)

 The most important factor;

 6.0 – 7.0 (alum); 5.5-8.5 (ferric iron);
 The lower pH, the higher the positive charge per
Al or Fe species;
 The higher pH, the larger dominant species and
hence the greater the tendency to form polymers;
more adsorption and bridging to form “sweep
floc”.
CHARACTERISTICS OF INORGANIC COAGULANTS
EXERCISE
A chemical supplier reports the concentration of stock
alum chemical as 8.37 percent as Al2O3 with a specific
gravity of 1.32. For a 30 mg/L alum dose applied to
treatment plant with a capacity of 43,200 m3/d (0.5 m3/s),
calculate
 The molarity of Al3+;
 The concentration of alum in the stock chemical as
mg/L Al2O3;
 The alkalinity consumed (as mg/L CaCO3);
 The amount of precipitate produced in mg/L and
kg/day; and
 The dosage of NaOH that would need to be added to
counteract the consumption of alkalinity by alum.
Given

Molecular weights:
Al=27, O=16, H=1, S=32, and Na=23 g/mol

1. Al2(SO4)3 ·14H2O 2Al(OH)3 + 6H+ + 3SO42- +

8H2O
2. Al2(SO4)3 ·14H2O + 6NaOH 2Al(OH)3 + 3NaSO4
+ 14H2O
3. Al2(SO4)3 ·14H2O + 3Ca(HCO3)2 2Al(OH)3 +
3CaCO3 + 6CO2 + 14H2O
 JAR TEST
 The jar test – a laboratory procedure to determine the optimum pH
and the optimum coagulant dose
 A jar test simulates the coagulation, flocculation and sendimentation
processes

Jar Test setup

 Determination of optimum pH

 Fill the jars with raw water sample (500 or 1000 mL) – usually 6 jars;
 Adjust pH of the jars while mixing using H2SO4 or NaOH/lime;
(pH: 5.0; 5.5; 6.0; 6.5; 7.0; 7.5)
 Add same dose of the selected coagulant (alum or iron) to each jar;
(Coagulant dose: 5 or 10 mg/L)
 Rapid mix each jar at 100 to 150 rpm for 1 minute. The rapid mix
helps to disperse the coagulant throughout each container;
 Reduce the stirring speed to 25 to 30 rpm and continue mixing for
15 to 20 mins;
 Turn off the mixers and allow flocs to settle for 30 to 45 mins;
 Measure the final residual turbidity in each jar;
 Plot residual turbidity against pH.
 Residual turbidity versus pH

Optimum pH: 6.3

The pH with the lowest residual turbidity will be the optimum pH

 Determination of optimum coagulant
dose

 Fill the jars with raw water sample (500 or 1000 mL) – usually 6 jars;
 Adjust pH of all jars at optimum (6.3 found from first test)
while mixing using H2SO4 or NaOH/lime
 Add different doses of the selected coagulant (alum or iron) to each
jar (Coagulant dose: 5; 7; 10; 12; 15; 20 mg/L)
 Rapid mix each jar at 100 to 150 rpm for 1 minute. The rapid mix
helps to disperse the coagulant throughout each container;
 Reduce the stirring speed to 25 to 30 rpm and continue mixing for
15 to 20 mins;
 Turn off the mixers and allow flocs to settle for 30 to 45 mins;
 Measure the final residual turbidity in each jar;
 Plot residual turbidity against coagulant dose.
 Residual turbidity versus dosage
Optimum coagulant dose: 12.5 mg/L

The coagulant dose with the lowest residual turbidity will be the
optimum coagulant dose
RAPID MIXING

To uniformly mix the coagulant

with colloidal matters present
in raw water so as to bring about
colloidal destabilization

Chemical
feeding

Inflow
 How to achieve rapid mixing

• Horizontal baffled tank

The water flows in a horizontal
direction. The baffle walls help L
to create turbulence when the
water hits the surface and thus W
facilitate mixing
Plan view (horizontal flow)
• Vertical baffled tank
The water flows in a
vertical direction. The
baffle walls help to create H
turbulence when the water
hits the surface and thus
facilitate mixing L
Isometric View (vertical flow)
• Hydraulic Jump: Hydraulic Jump creates turbulence and
thus help better mixing.

Coagulant

• In-line flash mixing

• Mechanical mixing
Back mix impeller flat-blade impeller

Inflow
Chemical
feeding
Chemical
feeding Inflow
In-line flash mixing
3.5 COAGULATION OF DISSOLVED
CONSTITUENTS
Natural organic matter (NOM)
 Particulate and dissolved organic matter, due
to biological activity.
 Have a wide range of molecular weight;
 “Disinfection by-product” (DBP) precursor;
 NOM is responsible for color;
 Measurement: TOC and DOC;
 Concentration: 1-50 mg/L as DOC;
ENHANCED COAGULATION
 The process of performing coagulation for the
purpose of achieving the removal of DBP
precursors (NOM) by decreasing pH and
increasing coagulant dosage.
 Mechanisms of coagulation of NOM:
 Adsorption onto aluminum hydroxide or ferric
hydroid floc;
 Formation of insoluble complexes (aluminum
or iron humates or fulvates).
DOSE REQUIREMENT FOR NOM
REMOVAL
THE IMPACT OF pH ON NOM REMOVAL
3.6 FLOCCULATION THEORY
DESIGN OF SLOW MIXING
(FLOCCULATION)
 Destabilized colloids from coagulation may settle
very slowly;
 In slow mixing process, particles are brought into
contact to promote agglomeration;
 Objective: provide increase in the number of
contacts between coagulated particles by gentle
agitation.
 Devices used to achieve gentle mixing:
 Mechanically driven paddles
 Baffled channels
o Microscale flocculation: for relatively
small particles which follow random
motion and collide with other particles
(Perikinetic flocculation)

o Macroscale flocculation : gentle

mixing causes velocity gradients that
cause collisions between suspended
particles (Orthokinetic flocculation)

o Differential settling: particles with

different size settle at different rates;
particles with different settling
velocities cause the particle to collide
and flocculate (Sedimentation)
MICRO- OR PERIKINETIC
FLOCCULATION
 Due to Brownie motion; colloidal particles: < 1µm.
 Perikinetic flocculation rate:

dN 4 2
J pk = =- α×k×T×N
dt 3μ

N: particle number concentration

µ: dynamic viscosity of water, N s/m2
kT = 4.045 x 10 -14 ergs
a: collision efficiency (0 - 1)
 MACRO- OR ORTHOKINETIC
FLOCCULATION
 Use mixing for aggregation of course-sized colloidal
particles: > 1µm;
 First-order kinetics in monodisperse system;
 Orthokinetic flocculation rate of a monodisperse system:
dN 4 GN
 d3  N
dt  
N 4
6
ln     G  t
N0 
N0 : initial colloid number concentration (number/volume of suspension).
: floc per unit of solution volume, cm3/L
d: particle diameter, cm
N: particle number concentration, L-1
G: velocity gradient, S-1
α: collision efficient factor
EXAMPLE
Calculate the time required to reduce the number of
particles by 50% under laminar conditions for macro-
scale flocculation, assuming first-order kinetics, for 1
µm particles. Assume the initial particle concentration
is 10,000/mL, G = 60 s-1, and α = 1.0.
SOLUTION
3.6 FLOCCULATION PRACTICE
AVERAGE VELOCITY GRADIENT G
G should be in the range of 20 to 70 s-1, and retention
time from 30 to 45 min

0.5
 P 
G 
  V 
where P = power input (W or Nm/s)
 = dynamic viscosity of liquid (Pa.s or Ns/m 2 )
V = reactor volume (m 3 )

79
SELECTION OF G AND GT VALUES
The total number of particle collisions is indicated as a
function of the product of the velocity gradient and
detention time (Gt)

2
0.5 0.5 0.5
 P   P   V  1  PV 
Gt    t      
  V    V   
Q Q   

80
TYPES OF FLOCCULATION
TYPES OF FLOCCULATORS

82
CV3
Horizontal-shaft paddle 501
(2008
flocculators -09)
Lect
ure 6:
Coag
ulati
on
and
TYPICAL DESIGN CRITERIA FOR HORIZONTAL-SHAFT
PADDLES AND VERTICAL-SHAFT TURBINES
VERTICAL TURBINE FLOCCULATOR
REYNOLDS NUMBER
Reynolds number is used to describe the different
flow regimes: laminar, transitional or turbulent
flow.
 MECHANICAL AGITATORS
 For highly turbulent flows, Re > 10,000
P = Npρn3d5
where P = power, W

86
 Np = power number of impeller, or impeller constant
 Np = f(w/d, impeller type)
 d = impeller diameter (m)
 n = impeller speed (rev. per sec)
 ρ = density of liquid, kg/m3
 For transitional to weakly turbulent regime, CV3
501
(2008
1000 < Re < 10,000, still ok to use eqn. -09)
Lect
 For laminar regime, Re < 1,000 ure 6:
Coag
Np = f(w/d, Re) ulati
on
and
HORIZONTAL PADDLE WHEEL FLOCCULATORS
HORIZONTAL SHAFT PADDLE
DESIGN OF PADDLES
Power required, P = (0.5CDAρv2)v
 A = total paddle plate area (m2)

91
 CD= drag coefficient (1.8 for flat plates)

 v = velocity of paddles relative to water;

~ 0.75 of paddle tip velocity, vp

 vp = 2 πrN, paddle tip velocity

 r = radius of rotation (m) CV3

501
 N = rotation speed of shaft, rps (2008
-09)
 ρ = density of water, 1000 kg/m3 Lect
ure
6:
Coag
ulati
on
and
EXAMPLE
Given HRT = 30 min, Q = 0.22 m3/s, vp = 0.8 m/s, r=1m,
µ=0.89*10-3 Ns/m2, assume G = 50 s-1
find V, P and A of flocculation tank.

92
Solution
 V = Qt = (0.22)(30 x 60) = 396 m3

 P = G2µV = (50)2(0.00089)(396) = 881 W

 v= 0.75vp= 0.75*0.8=0.60 m/s

 Total area of paddle plates A = P / (0.5CDρv3) CV3

501
= 881 / (0.5 x 1.8 x 1000 x 0.63 ) = 4.53 m2 (2008
-09)
Lect
ure
6:
Coag
ulati
on
and
EXAMPLE
Given Q = 0.22 m3/s, mixing time = 20 sec,
At 25°C, µ = 0.89 x 10-3 Ns/m2 , G ~ 1000 s-1

93
Find, volume V and power P requirement
Solution:
 V = Qt = 0.22 x 20 = 4.4 m3

 P = G2µV = (1000)2(0.89 x 10-3)(4.4) = 3916 W

To achieve complete mixing within 20sec, and for a CV3

reactor of 4.4 m2, install a mixer/impeller that can 501
(2008
impart ~ 4,000 W. -09)
Lect
ure
6:
Coag
ulati
on
and