Coagulation and Flocculation

Natural surface waters and wastewaters contain

inorganic and organic particles.

Size of particles
 Suspended: generally larger than 1.0 μm
in water and
 Colloidal: vary from about 0.001 to 1 μm
wastewater

Inorganic Organic
a) Clay a) Fine colloidal organics
b) Silt b) Bacteria, Algae and Protozoan
c) Mineral oxides c) Detritus litter

(1) Reduce the clarity

Removal of (2) Be infectious agents
Particulates is (3) Have toxic compounds adsorbed to their
necessary external surfaces
(4) Contribute to COD and BOD load
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 Coagulation and Flocculation

COAGULATION: Addition of a chemical coagulant or

coagulants for the purpose of conditioning the suspended,
colloidal, and dissolved matter for subsequent processing
by flocculation or to create conditions that will allow for the
subsequent removal of particulate and dissolved matter.

Requires 10 s
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 Coagulation and Flocculation

FLOCCULATION: Aggregation of destabilized particles

(particles from which the electrical surface charge has been
reduced) and precipitation products formed by the addition
of coagulants into larger particles known as flocculant
particles or, more commonly, ‘‘floc.’’

Requires 20 to 45 min
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 Coagulation and Flocculation
Coagulation can be performed by addition of hydrolyzing
chemicals to water/wastewater

Aluminum, Ferric, and Organic polymers (polymers with

Ferrous salts multiple charge-conferring functional groups)

 Destabilization of suspended and colloidal particles (reducing

the repulsive forces and/or forming bridges between them)

 Adsorption and/or reaction of portions of the colloidal and

dissolved NOM to particles.
 Creation of flocculant particles that will sweep through the
water to be treated, enmeshing small suspended, colloidal,
and dissolved material as they settle.

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 Coagulation and Flocculation
Flocculation can be performed by microflocculation (also
known as perikinetic) and macroflocculation (also known
as orthokinetic flocculation)

Microflocculation Macroflocculation

Particle aggregation is Particle aggregation is brought

brought about by the about by inducing velocity
random thermal motion gradients and mixing in the
of fluid molecules fluid containing the particles to
(known as Brownian be flocculated or by differential
motion). settling in which large particles
overtake small particles to form
larger particle.

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 Coagulation and Flocculation
Process issues

 The type and concentration of coagulants and

flocculant aids.
 The mixing intensity and the method used to disperse
chemicals into the water for destabilization,
 The mixing intensity and time for flocculation

Electrical properties of particles

Surface charge, which contributes to relative stability,

causing particles to remain in suspension without
aggregating for long periods of time.

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 Coagulation and Flocculation
Stability of Particles in Water
(Surface charge arises in four principal ways)

Replacement of a metal atoms with

one with lower valence

Isomorphous replacement
(crystal imperfections)

Imperfections that occur in the

Structural imperfections formation of the crystal and broken
bonds on the crystal edge

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 Coagulation and Flocculation
Stability of Particles in Water
(Surface charge arises in four principal ways)

Adsorption of NOM that are

negatively charged on the particle
Preferential adsorption of surface
specific ions

Surface functional groups (e.g.,

hydroxyl) and their charge
depends on pH.
Ionization of inorganic
groups on particulate
surfaces

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 Coagulation and Flocculation
Stability of Particles in Water
(Zero point of charge)

The pH corresponding to a surface charge of zero is

defined as the zero point of charge (ZPC). Above the
ZPC the surface charge will be negative (anionic), and
below the ZPC the charge will be positive (cationic).

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 Coagulation and Flocculation
Stability of Particles in Water
(Electrical Double Layer (EDL) [Stern + Diffusion layers])

Helmholtz (Stern) layer

A layer of cations that bind
tightly to the surface of a
negatively charged particle to
form a fixed adsorption layer.

Diffusion layer
300 ˚A
A layer with net negative charge
and electric field beyond the
Helmholtz layer that attracts
cations (over the bulk solution
concentration) and repels
anions causing cations and
anions move about under the
influence of diffusion.
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 Coagulation and Flocculation
Stability of Particles in Water
(Measurement of surface charge)

1) Electrophoresis
2) Electroosmosis Electrokinetic
3) Sedimentation potential (Dorn effect) Phenomena
4) Streaming potential

the surface charge on a particle can be measured indirectly

using one of the four electrokinetic phenomena.

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 Coagulation and Flocculation
Stability of Particles in Water
(Zeta potential)

Electrical potential between the

actual shear plane and the bulk
solution is what is measured by
electrophoretic measurements.

Empirically, when the absolute value of 300 ˚A

the zeta potential is reduced below
approximately 20 mV, rapid flocculation
occurs. Zeta potential changes with
1) Size and shape of the particle
2) Number of charges on the particle
3) Strength of the electric field
4) Nature of the ions in the diffuse layer

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 Coagulation and Flocculation
Stability of Particles in Water
(Particle stability)

Repulsive force Attractive force

(electrostatic) (van der Waals)

Van der Waals attractive forces

(<∼20 kJ/mol) are strong enough
Electrostatic repulsion to overcome electrostatic
occurs, because particles in repulsion, but they are unable to
water have a net negative do so because electrostatic
surface charge. repulsive forces and the EDL
extend further into solution than
do the van der Waals forces.

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 Coagulation and Flocculation
Stability of Particles in Water
(Particle stability)

Particle-Particle interaction
Derjaguin, Landau, Verwey and Overbeek (DLVO) model

Clearly, if colloidal particles

are to be flocculated by
microflocculation, the
repulsive force must be
reduced as in case 2. With
the addition of a coagulant,
which reduces the extent of
the electrical double layer,
rapid flocculation can occur.

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 Coagulation and Flocculation
Stability of Particles in Water
(Compression of the electrical double layer)

If the electrical double layer is compressed, particles in water

will come together as a result of Brownian motion and remain
attached due to van der Waals forces of attraction. As the ionic
strength of a solution is increased, the extent of the double
layer decreases, which in turn reduces the zeta potential
It is possible to reduce the thickness of the EDL by
Ionic increasing the ionic strength, but is not a practical method
strength because the required ionic strengths are greater than are
considered acceptable in potable water.

Critical Coagulation Concentration (CCC) is the ionic

concentration that results in the reduction of the EDL so
Effect of flocculation can occur. It depends on the type of particulate
counterions as well as the dissolved ions. According to the DLVO
theory, the CCC is inversely proportional to the sixth power
of the charge on the ion.
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 Coagulation and Flocculation
Coagulation Theory
Mechanisms that can be exploited to achieve
particulate destabilization include
(1) Compression of the electrical double layer
(2) Adsorption and charge neutralization
(3) Adsorption and interparticle bridging
(4) Enmeshment in a precipitate, or ‘‘sweep floc.’’
Particulates can be destabilized by adsorption of
Adsorption and
oppositely charged ions or polymers. Higher dosages
charge neutralization cause charge reversal, particle stability.

Polymer bridging is a complex process. polymer

chains (MW105 to 107) adsorb on particle surfaces at
Adsorption and one or more sites along the polymer chain. The rest
interparticle bridging of the polymer may remain extended into the solution
and adsorb on available surface sites of other
particles.
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 Coagulation and Flocculation
Coagulation Theory
Mechanisms that can be exploited to achieve
particulate destabilization include
(1) Compression of the electrical double layer
(2) Adsorption and charge neutralization
(3) Adsorption and interparticle bridging
(4) Enmeshment in a precipitate, or “sweep floc”

When high enough dosages are used, aluminum

and iron form insoluble precipitates and particulate
matter becomes entrapped in the amorphous
Enmeshment in a precipitates. In general, the sweep floc mechanism
precipitate, or does not depend on the type of particle, and, thus,
the same dosage of coagulant is required for
‘‘sweep floc” sweep floc formation regardless of the type of
particles that may be present (in the absence of
NOM).
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 Coagulation and Flocculation
Coagulation Practice
A brief handout is provided for the reactions and
characteristics of most used coagulants.

Jar Testing
for Coagulant
Evaluation
[Langelier (1921)]

(1) Turbidity or suspended solids removal;

(2) NOM removal as measured by dissolved organic carbon (DOC) or a
surrogate measure of dissolved NOM, such as UV at 254 nm;
(3) Residual dissolved coagulant concentrations of Fe or Al coagulants;
(4) Sludge volume that is produced;
(5) Filterability test if direct filtration is to be used.
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 Coagulation and Flocculation
Coagulation Practice

Jar Testing
for Coagulant
Evaluation

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 Coagulation and Flocculation
Coagulation Practice

Jar Testing
for Coagulant
Evaluation

For the lowest particle

concentration, S1,
particles are removed
by sweep flocculation
Addition of flocculant aid like clay of bentonite can be considered.
(precipitation) because
the concentration is too
low for them to
flocculate and settle.

These particles are also destabilized by the hydrolysis products of the

coagulant. The particle concentration S1 may be a good candidate for
direct filtration or dissolved air flotation for liquid–solid separation.
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 Coagulation and Flocculation
Coagulation Practice

Jar Testing
for Coagulant
Evaluation
At a slightly higher
particle concentration,
Addition of flocculant aid like clay of bentonite can be considered.
S2, some flocculation and
settling occurs in zone 2
by adsorption and charge
neutralization. However,
the concentration is too
low for effective
flocculation.

If more coagulant is added, the particles stabilize and the turbidity increases,
as shown in zone 3. As the coagulant dosage is increased even further, sweep
flocculation is again observed but at a lower coagulant concentration than for a
particle concentration S1 because the particle concentration is higher.
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 Coagulation and Flocculation
Coagulation Practice

Jar Testing
for Coagulant
Evaluation
At a higher particle
concentration, S3, nearly
complete removal by
charge neutralization
occurs in zone 2 and the
particles stabilize at
higher coagulant
dosages.

Sweep flocculation occurs in zone 4, and it occurs at lower coagulant dosages

than for particle concentration S2 or S1. Sweep flocculation occurs because a
substantial portion of the floc volume comes from the particles, and this allows
for effective flocculation at lower coagulant dosages.
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 Coagulation and Flocculation
Coagulation Practice

Jar Testing
for Coagulant
Evaluation
For the highest particle
concentration, S4, the
sweep floc and charge
neutralization regions
merge because the
coagulant concentration
required to destabilize
particles coincides with
the onset of precipitation.

Another noteworthy effect is that zone 2 starts at successively higher

coagulant dosages as the particle concentration increases. As a result, the
charge neutralization region is said to exhibit stoichiometry.
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 Coagulation and Flocculation
Alternative Techniques to Reduce Coagulant Dose

Several techniques have been evaluated to reduce

the coagulant dose, including
(1) Preozonation;
(2) The use of selective ion exchange resins;
(3) The use of electrical field

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 Coagulation and Flocculation
Coagulation of Dissolved Constituents

Undesirable
consequences of pH
adjustment should be
considered.

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 Coagulation and Flocculation
Coagulation of Dissolved Constituents
Determination of Coagulant Dose for DOC Removal
Edwards (1997) developed an empirical model to
estimate DOC removal during enhanced coagulation.

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 Coagulation and Flocculation
Coagulation of Dissolved Constituents
Determination of Coagulant Dose for DOC Removal
Edwards (1997) developed an empirical model to
estimate DOC removal during enhanced coagulation.

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 Coagulation and Flocculation
Coagulation of Dissolved Constituents
Determination of Coagulant Dose for DOC Removal

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 Coagulation and Flocculation
Coagulation of Dissolved Constituents
Determination of Coagulant Dose for DOC Removal

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 Coagulation and Flocculation
Coagulation of Dissolved Constituents
Determination of Coagulant Dose for DOC Removal

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Coagulation and Flocculation
Flocculation Practice

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 Coagulation and Flocculation
Flocculation Practice

Today’s flocculation installations can be divided into two groups:

(1) mechanical and hydraulic. In mechanical flocculation horizontal paddles
and vertical turbines have become the most common configurations for the
prime mover, although new innovations continue to be developed.
(2) No particular arrangement dominates in hydraulic flocculation. Occasionally
designers have used agitation with air or pumped water jets to create the
velocity gradients for flocculation, but these efforts have met with limited
success.

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Coagulation and Flocculation
Flocculation Practice

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Coagulation and Flocculation
Flocculation Practice

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 Coagulation and Flocculation
Flocculation Practice

The choice among these three alternatives is usually driven by personal preference, by
downstream processes, and by the level of operational expertise available.

Provided there is sufficient flocculation time, the flocs produced by hydraulic flocculation
are virtually always of settleable size. With either type of mechanical mixer, large flocs
suitable for sedimentation can be attained by tapering down the power input in
subsequent flocculators. As a result, variable-speed drives are usually provided. Often
two- or three-speed drives, are all that are necessary.
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 Coagulation and Flocculation
Flocculation Practice
Design Approach

The basic design criteria for mechanical flocculators are

1) RMS velocity gradient G
2) Hydraulic detention time t
Short flocculation times are often used for direct filtration (10 to 20 min)
Conventional treatment require more time (20 to 30 min)
Longer flocculation times are also required in colder climates

When vertical turbine

impellers are used, it is
wise to stick to a nearly
cubical shape
flocculation chamber and
to locate the impeller at
approximately two thirds
of the chamber’s water
depth.
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 Coagulation and Flocculation
Flocculation Practice
Design Approach (Vertical Turbine Flocculators)
(1) Radial flow impellers
(2) Axial flow impellers.

pump downward
pump upward.
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 Coagulation and Flocculation
Flocculation Practice
Design Approach (Vertical Turbine Flocculators)
Important design considerations for vertical turbine impellers are

(1) The displacement capacity (the rate at

which the impeller pumps water)

(2) The power consumption

(3) The pumping head.

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 Coagulation and Flocculation
Flocculation Practice
Design Approach (Vertical Turbine Flocculators)

Virtually all flocculation impellers operate in the turbulent-flow regime.

For the vertical turbines used in flocculation, full turbulence is
developed at Reynolds numbers of 10,000 and greater.

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 Coagulation and Flocculation
Flocculation Practice
Design Approach (Vertical Turbine Flocculators)

 Radial flow turbines and flat-bladed turbines move through the water, creating
substantial trailing vortices that contributes significantly to floc breakup.
 Long pitch blade turbines have become more popular, but, even these produce
substantial trailing vortices.
 Today hydrofoils, or pitched-blade turbines with cambered blades (blades with
an upper surface shaped like an airplane wing), are the impellers of choice.

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 Coagulation and Flocculation
Flocculation Practice
Design Approach (Vertical Turbine Flocculators)

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 Coagulation and Flocculation
Flocculation Practice
Design Approach (Vertical Turbine Flocculators)

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Coagulation and Flocculation
Flocculation Practice

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Coagulation and Flocculation
Flocculation Practice

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 Coagulation and Flocculation
Flocculation Practice
Design Approach (Horizontal Paddle Wheel Flocculators)

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 Coagulation and Flocculation
Flocculation Practice
Design Approach (Horizontal Paddle Wheel Flocculators)
The power input to the
water by horizontal
paddles..

Here, vR is usually assumed to

be 70 to 80 percent of the
paddle speed without tank
baffles. With tank baffles, 100
percent of the paddle speed is
considered.

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 Coagulation and Flocculation
Flocculation Practice
Design Approach (Horizontal Paddle Wheel Flocculators)

It is difficult to achieve 50 to 60 s−1 with paddle wheel flocculators.

Typical values of G for paddle wheel flocculators are 20 to 50 s−1.

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Coagulation and Flocculation
Flocculation Practice

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Coagulation and Flocculation
Flocculation Practice

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Coagulation and Flocculation
Flocculation Practice

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Coagulation and Flocculation
Flocculation Practice

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Coagulation and Flocculation
Flocculation Practice

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Coagulation and Flocculation
Flocculation Practice
Design Approach (Hydraulic Flocculation )

1- Baffled channels
2- Hydraulic-jet
3- Coarse-media

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Coagulation and Flocculation
Flocculation Practice
Design Approach (Hydraulic Flocculation )

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Coagulation and Flocculation
Flocculation Practice
Design Approach (Hydraulic Flocculation )

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 Coagulation and Flocculation
Flocculation Practice
Design Approach (Diffuser Walls)

Diffuser walls are used to to place a hydraulic division between flocculation and
sedimentation basins, as well as in other situations where an even velocity profile
is required and backmixing is undesirable.

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 Coagulation and Flocculation
Flocculation Practice
Design Approach (Diffuser Walls)

Diffuser walls are used to to place a hydraulic division between flocculation and
sedimentation basins, as well as in other situations where an even velocity profile
is required and backmixing is undesirable.

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Coagulation and Flocculation
Flocculation Practice
Design Approach (Diffuser Walls)

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