COAGULATION

The primary purpose in surface-water treatment is chemical

clarification by coagulation and mixing, flocculation, sedimentation,
and filtration. Specifically, coagulation and flocculation work to
destabilize particles and agglomerate dissolved and particulate matter.

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Materials present in raw water may vary in size, concentration, and
type. Dispersed substances in the water may be classified as
suspended, colloidal, or solution.

• Molecules sizes smaller than 1 nm

• Colloids generally with dimensions between 1 nm and 1 µm
• Suspended matter having sizes larger than 1 µm.

Colloids: humic acids, proteins, clay, silica and viruses

Suspended matter: Bacteria, algae, silt, sand and organic debris

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Suspended particles may vary in mass and size and are dependent on
the flow of water. High flows and velocities can carry larger material. As
velocities decrease, the suspended particles settle according to size and
mass.

Other materials may be in solution; for example, salts dissolve in water.

Particles in the colloidal state does not dissolve, but the particles are so
small they will not settle out of the water. Color is mainly due to
colloids or extremely fine particles of matter in suspension.

Colloidal and solute particles in water are electrically charged. Because

most of the charges are alike (negative) and repel each other, the
particles stay dispersed and remain in the colloidal or soluble state.
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Suspended matter will settle without treatment, if the water is still
enough to allow it to settle. The rate of settling of particles can be
determined, as this settling follows certain laws of physics; however,
much of the suspended matter may be so slow in settling that the
normal settling processes become impractical, and if colloidal particles
are present settling will not occur.

Water drawn from a raw water source often contains many small
unstable particles; therefore, sedimentation alone is usually an
impractical way to obtain clear water in most locations, and another
method of increasing the settling rate must be used: coagulation, which
is designed to convert stable particles to unstable particles.

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The term coagulation refers to the series of chemical and mechanical
operations by which coagulants are applied and made effective.
These operations are comprised of two distinct phases:
(1) rapid mixing to disperse coagulant chemicals by violent agitation
into the water being treated,
(2) flocculation to agglomerate small particles into well-defined floc by
gentle agitation for a much longer time.

Coagulation results from adding salts of iron or aluminum to the water.

The coagulant must be added to the raw water and perfectly
distributed into the liquid; such uniformity of chemical treatment is
reached through rapid agitation or mixing.

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The direct use of gravity in the form of straight forward sedimentation -
where the determining factors are:
• Particle size
• Specific weight (ρS/ρL)

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How can we increase the sedimentation rate of small particles?

d 2 g  p   w 
Vt 
18

• Increasing d (stick particles together)

• Increasing g (centrifuge)
• Increasing density difference (dissolved air flotation)
• Decreasing viscosity (increasing temperature)

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Surface charge on a particle in water
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Particle interactions
• Electrostatic repulsion
• In most surface waters, colloidal surfaces are negatively charged
• Charged particles cause stable suspension
• Van der Waals force
• An attractive force
• Decays more rapidly with distance than the electrostatic force
• Is a stronger force at very close distances

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Repulsion due to Zeta potential

• Increase kinetic energy of particles

• Increasing temperature
Net resultant force • Stirring

+ ++ + ++
+ + + + Distance
+ ++ + ++
+ +

• Decrease magnitude of energy barrier

• change the charge of the particles
• introduce positively charged particles
Attraction due to van der Waals Forces
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Effect of solution concentration and charge (Z) on double layer

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Coagulation mechanisms:
• Adsorption of cations onto negatively charged particles
• Decrease the thickness of the layer of counter ions
• Sweep coagulation
• Interparticle bridging

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Common coagulants:
• Alum (aluminum sulfate)-Al2(SO4)3.18H2O
• Sodium aluminate-NaAlO2
• Ferric sulfate-Fe2(SO4)3.9H2O
• Ferrous sulfate-FeSO4.7H2O
• Ferric chloride-FeCl3
• Polymers

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Frequently used inorganic coagulants

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The chemistry is complex with many possible species formed such as
AlOH+2, Al(OH)2+, and Al7(OH)17+4

The primary reaction produces Al(OH)3

Al2(SO4)3 + 6H2O2Al(OH)3 + 6H+ + 3SO4-2

Aluminum hydroxide [Al(OH)3] forms amorphous, gelatinous flocs that

are heavier than water. These flocs entrap particles as the flocs settle
(sweep coagulation)

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Iron can be used as either the sulfate salt (Fe2(SO4)3.nH2O) or the
chloride salt (FeCl3.nH2O).

The reaction produces Fe(OH)3

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A number of factors influence the coagulation process—pH, turbidity,
temperature, alkalinity, and the use of polymers. The degree to which
these factors influence coagulation depends on the coagulant use. The
raw water conditions, optimum pH for coagulation, and other factors
must be considered before deciding which chemical is to be fed and at
what levels.

To determine the correct chemical dosage, a jar test or coagulation test

is performed. Jar tests (widely used for many years by the water
treatment industry) simulate full-scale coagulation and flocculation
processes to determine optimum chemical dosages.

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The test conditions are intended to reflect the normal operation of a
chemical treatment facility.

The test can be used to:

• Select the most effective chemical
• Select the optimum dosage
• Determine the value of a flocculant aid and the proper dose

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Best pH range for coagulation is 5 to 7. Coagulants react with the alkalinity in
the water and serves as a buffer to prevent pH change. If alkalinity in source
water is too low, complete precipitation of coagulant may not occur.
Alkalinity can be increased by addition of lime.

• The optimum pH range for alum is approximately 5.5 to 7.7 with adequate
coagulation possible between pH 5 and 9 under some conditions.
• Ferric salts generally have a wider pH range for effective coagulation than
aluminum, that is, pH ranges from 4 to 9.
• Prehydrolyzed metal salts (polyaluminum chloride, polyaluminum sulfate,
and polyiron chloride) can be used over a pH range of 4.5 to 9.5.

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Solubility diagram for amorphous aluminum hydroxide Solubility diagram for amorphous ferric hydroxide

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Estimate the amount of alkalinity (in mg/L) consumed from the addition of 100
mg/L of alum.

6 moles of HCO3 are consumed for each mole of alum added.

The moles/L of alum added:

The moles/L of HCO3 consumed:

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When alum is placed in water, a chemical reaction occurs that produces
positively charged aluminum ions. The overall result is the reduction of
electrical charges and the formation of floc, which when properly
formed, will settle. These two destabilizing factors are the major
contributions that coagulation makes to the removal of turbidity, color,
and microorganisms.

The formation of floc is the first step of coagulation; for greatest

efficiency, rapid, intimate mixing of the raw water and the coagulant
must occur. After mixing, the water should be slowly stirred so the very
small, newly formed particles can attract and enmesh colloidal
particles, holding them together to form larger floc. This slow mixing is
the second stage of the process (flocculation).
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Methods of Mixing
Mechanical mixing
With paddles, turbines, and propellers
Versatile and reliable
Use greatest amount of energy

Hydraulic mixing
With baffles or throttling valves if sufficient velocity to cause turbulence
Turbulence mixes chemicals with the water

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In-line blenders
Coagulant added directly to the water being treated through a diffuser in a pipe
Can provide rapid dispersion of chemical
No significant head loss
Considerably low energy consumption

Static mixer
Mechanical in-line blender

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In-Line Mechanical Mixing
The following design criteria may be used in selection of in-line
mechanical mixers: G in the range 3,000 to 5,000 s-1, t of about 0.5 s,
and headloss of 0.3 to 0.9 m.

In-Line Static Mixing

This mixer consists of a pipe with in-line helical vanes that rotate and
split the flow to increase turbulence. The vanes are segmented so that
the number of vanes may be adjusted to fit local conditions.

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Velocity Gradient
The concept of the average hydraulic gradient, G (s−1) was developed by
Camp and Stein in 1943 to characterize mixing in flocculation basins,
and the G value is now used worldwide to characterize mixing in a wide
range of environmental engineering applications. Camp and Stein
termed this the absolute velocity gradient and related this to work
done per unit volume per unit time.

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The velocity gradient may be thought of as the amount of shear taking
place; the higher the G value, the more violent the mixing. The velocity
gradient is a function of the power input into a unit volume of water.

Different velocity gradients are appropriate for different processes.

Coagulation requires very high velocity gradients. Flocculation requires
a velocity gradient high enough to cause particle contact and to keep
the flocs from settling but low enough to prevent the flocs break.

P is power consumed
V is tank volume
µ is dynamic viscosity of the water

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 Mechanical Mixing

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The power imparted to the liquid in a baffled tank by an impeller may be described
by the following equation for fully turbulent flow developed by Rushton (1952).

P: power, W
Np: impeller constant (also called power number)
n: rotational speed, revolutions/s
Di: impeller diameter, m
r: density of liquid, kg/m3

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Design a cylindrical flash mixing basin by determining the basin volume, tank
diameter, dimensions, required input power, impeller diameter from
manufacturer’s data provided below, and its rotational speed using the following
parameters:
Design flow rate = 11.5 x103 m3/d
Rapid mix t = 5 s
Rapid mix G = 600 s-1
Water temperature = 5 °C
Impeller is at one-third the water depth
From manufacturer’s data, the following impellers are available

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Conversion of 11.5 x103 m3/d to m3/s

The volume of the rapid mix basin

Assuming H/T =2.0, that is H=2 T

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The impeller is at 1/3 water depth

The required input water power (µ=1.519 x103 Pa.s)

Transfer of motor power to water power is about 80%

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The rotational speed

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FLOCCULATION
Flocculation follows coagulation in the conventional water treatment
process. Flocculation is the physical process of slowly mixing the
coagulated water to increase the probability of particle collision;
unstable particles collide and stick together to form fewer larger flocs.

Effective mixing reduces the required amount of chemicals and greatly

improves the sedimentation process, resulting in longer filter runs and
higher quality finished water.

Insufficient mixing will result in ineffective collisions and poor floc

formation. Excessive mixing may tear apart or shear the floc that has
been formed.
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The goal of flocculation is to form a uniform, dense, tenacious floc that
entraps the fine, suspended, and colloidal particles and carries them
down rapidly in the settling basin.

Proper flocculation requires from 15 to 45 minutes. The time is based

on water chemistry, water temperature, and mixing intensity.
Temperature is the key component in determining the amount of time
required for floc formation.

To increase the speed of floc formation and the strength and weight of
the floc, polymers are often added.

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Flocculation is normally accomplished with one of the following
systems:
• Vertical turbine mixing similar to that used in flash mixing,
• Paddle flocculator,
• Baffled chamber

The paddle flocculator has been the design choice for numerous plants.
They are especially chosen for conventional treatment when a high
degree of solids removal by sedimentation is desired.

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The flocculation basin should be divided into at least three
compartments. The velocity gradient is tapered so that the G values
decrease from the first compartment to the last.

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 Types of Flocculators

Horizontal Vertical
Submerged mechanics Requires less maintenance
Propeller, paddle, or turbine types

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Flocculation Basins
Rectangular for horizontal flocculators
Nearly square for vertical flocculators
Compartmentalized basis achieve best flocculation
Separated by baffles
Prevents short circuiting

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Gt values for flocculation

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Paddle Flocculator
The power input to the water by horizontal paddles may be estimated as:

P = power imparted, W
CD = coefficient of drag of paddle
Ap = cross-sectional area, m2
vp = relative velocity of paddles with respect to fluid, m/s

The velocity of the paddles may be estimated as:

k = constant 0.75
r = radius to centerline of paddle, m
n = rotational speed, rps

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Enhanced Coagulation
Process designed to remove NOM from water by adjusting both the
coagulant dose and the pH. Differs from “sweep” method where pH
range is achieved by overdosing the coagulant.

Natural organic matter comprised of organic acids called humic

substances which composed of humic and fulvic acids. Fulvic and humic
substances in water are negatively charged. Negative charge is
neutralized and destabilized by positively charged coagulants.
Destabilized particles come together and form larger floc particles that
can be settled out.

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Characteristics of NOM, algal and kaolin systems

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SEDIMENTATION
After raw water and chemicals have been mixed and the floc formed,
the water containing the floc flows to the sedimentation or settling
basin. Sedimentation is also called clarification.

Sedimentation removes settleable solids by gravity. Water moves

slowly though the sedimentation tank/basin with a minimum of
turbulence at entry and exit points with minimum short-circuiting.

Sludge accumulates at the bottom of the tank/basin. Typical tanks or

basins used in sedimentation include conventional rectangular basins,
conventional center-feed basins, peripheral-feed basins, and spiral-flow
basins.

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 Rectangular center feed radial flow

peripheral feed with radial flow peripheral feed with spiral flow

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The easiest separation process to be developed for the continuous
clarification of particles from water is a horizontal settling tank.

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Consider a tank L (m) long, D (m) deep and W (m) wide which is
operated at a flow rate of Q m3hr−1. A particle at the inlet to the tank
must fall to the bottom of the tank in the time it takes the flow to exit
the tank to be removed. The time taken to fall the depth of the tank is

And the time for the water to travel the length of the tank is

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Combining the above expressions yields

Where L×W is the cross-sectional area of the tank such that Q/(L×W) is
the surface loading rate and represents the key design parameter for
sedimentation. If the actual settling velocity is lower than the hydraulic
loading rate the particle will be entrained in the flow and not be
retained.

An important consequence of the above is that in theory the depth of

the settlement tank is not important in deciding the performance of a
sedimentation process.
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Horizontal flow clarifiers in (a) horizontal or (b) radial configuration

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Increasing the particle density, or reducing the distance a particle must
fall prior to removal, can accelerate the clarification process.

To reduce the distance the particle must fall, a series of inclined plates
or tubes are placed in a rectangular horizontal flow settling basin.

The plates or tubes are inclined to a degree that allows the collected
solids to slide down the surface to the sludge zone. Typically the tube is
a square, about 5 cm on each side, and the angle is about 60°.

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Lamella plate clarifier

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Typical sedimentation tank overflow rates

Typical weir hydraulic loading rates

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Horizontal flow velocities must be controlled to avoid turbulence,
backmixing, and scour of particles from the sludge. Velocities of 0.6 to 1.2
m/min have been found to be acceptable for basin depths of 2 to 4.3 m. Reynolds
and Froude numbers can be used to check on turbulence and backmixing.

The Reynolds number is determined as:

The Froude number is determined as:

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