Coagulation and Flocculation

Typical treatment train for a surface water

treatment plant.
Particulates in Water
Removal of particles is required because they can
• (1) reduce the clarity of water to unacceptable
levels (i.e., cause turbidity) as well as impart
colour to water (aesthetic reasons),
• (2) be infectious agents (e.g., viruses, bacteria,
• and protozoa), and
• (3) have toxic compounds adsorbed to their
external surfaces.
Characteristics of Particles
• Colloidal and suspended particles have a surface
charge. This charge causes the particles to remain in
suspension without aggregating for long periods of
time.
• Given enough time, particles will flocculate and settle.
• However, the aggregation process is very slow, and
the particles cannot be removed by sedimentation in
a reasonable amount of time
• The principal mechanism controlling stability is
electrostatic repulsion.
 When the surface potentials are
high, the repulsion is strong even
at large separations, and particles
do not collide

When the surface potentials are

low, the particles can approach
close enough to collide and stick
• Eliminating the repulsive forces is an essential
step in the removal of colloids from water.

• Reducing or eliminating the repulsive forces so

that particles have the opportunity to stick to
each other is known as destabilization
Coagulation / Flocculation
• Coagulation: Formally, means making particles
“sticky” (rapid mix step);
• Flocculation: Causing collisions among sticky
particles (slow mix step), to form fewer, larger
ones

• Suspensions in which most particles remain in the

water are “stable,” so coagulation is sometimes
referred to as “particle destabilization.”
Coagulation Mechanisms
• Adsorption and Charge Neutralization. Hydrolyzed metal
salts, prehydrolyzed metal salts, and cationic polymers
have a positive charge. They destabilize particles through
charge neutralization.
• Adsorption and Interparticle Bridging. polymer chains
adsorb on particle surfaces. The adsorption is a result of
(1) coulombic, charge-charge interactions, (2) dipole
interaction, (3) hydrogen bonding, and (4) van der Waals
forces of attraction.
• Enmeshment in a Precipitate. With doses exceeding
saturation for the metal hydroxide, aluminium and iron
salts form insoluble precipitates and particulate matter is
entrapped in the precipitate. This type of destabilization is
described as sweep coagulation
Coagulation Chemistry
• Mechanism 1. Adsorption and Charge neutralisation
• Alum [Al2(SO4)3nH2O] and ferric chloride (FeCl3) dissociate to
release highly charged ions.
Al2(SO4)3nH2O 2 Al3+ + 3 SO42- + nH2O
FeCl3 Fe3+ + 3 Cl-
• These ions bind either directly to particle surfaces (adsorb)
or to NOM on those surfaces.
• They reduce the negative charge associated with the
particles and reduce repulsion. Ideally, the charge is brought
to near zero, and repulsion is almost eliminated.
Mechanism 2 : Enmeshment in a Precipitate
• At higher concentrations and pH, solids can
precipitate and enmesh the colloids in a “sweep floc”.

 Al3+ + 3 OH-  Al(OH)3(s)

 Fe3+ + 3 OH-  Fe(OH)3(s)
Mechanism 3: Adsorption and Interparticle Bridging
Polymers can induce coagulation by bridging
between particles
Coagulation Practice
• Selection of the type and dose of coagulant
depends on:
1) the characteristics of the coagulant
2) the concentration and type of particles
3) concentration and characteristics of NOM
4) water temperature
5) and water quality.
Coagulant Chemicals
• Alum is the most widely used coagulant chemical
but ferric chloride or ferric sulphate forms a
better-settling floc in some waters
• Polyaluminum chloride often produces a better-
settling floc in colder waters and often results in
lower dosages, thereby producing less sludge
than alum and ferric coagulants.
• Sludge quantity and disposal are important
considerations in selecting the coagulant to be
used.
Selection of coagulant chemicals
• Based on based on
• economic considerations
• reliability,
• safety, and chemical storage considerations.
• The best method of determining treatability, the most
effective coagulants, and the required dosages is to
conduct bench-scale and, in some cases, pilot tests.
• Jar tests can be used to determine treatability and
estimate chemical dosages. If possible, testing should
cover all critical seasonal conditions.
Characteristics of coagulants
• They are nontoxic at the working dosage.
• They have a high charge density.
• They are insoluble in the neutral pH range.
Coagulant Chemical formula Molecular weight
Aluminium sulphate AL2(SO4)3.14H2O 594
Sodium aluminate Na2Al2O4 164
Aluminium chloride AlCl3 133.5
Ferric chloride FeCl3 162.5
Ferric sulphate Fe2(SO4)3 400
Impact of pH on coagulation
• Control of pH and alkalinity is an essential aspect
of coagulation. The optimum pH for coagulation
varies but is generally within the following ranges
for turbidity removal:
Alum: pH 5.5 to 7.5; typical pH 7.0
Ferric salts: pH 5.0 to 8.5; typical pH 7.5
• It can be necessary to adjust the pH of some
source waters to achieve optimum coagulation.
The pH is often lowered by adding carbon dioxide
or an acid.
Impact of pH on coagulation
• There are a number of secondary impacts of using
higher coagulant dosages and lower pH values for
enhanced coagulation:
• Increased solids. The higher coagulant dosages
directly result in increased sludge volumes.
• Increased concrete-metal corrosion. The lower pH of
the coagulated water will be significantly more
aggressive on concrete and metals
• If pH is lowered to improve coagulation, it is typically
necessary to raise the pH in the final effluent from the
plant to provide a less corrosive finished water.
Impact of pH
• The operating region for aluminum hydroxide
precipitation is in a pH range of 7.0 to 8.0 and an alum
dose from 20 to 60 mg/L. The minimum alum
solubility occurs at a pH of about 6.2 at 25◦C.
• The ferric species are more insoluble than aluminum
species and are also insoluble over a wider pH range.
• Ferric ion is often the coagulant of choice to aid
destabilization in the lime-softening process, which is
carried out at higher pH values (pH 9)
Impact of Alkalinity
• The optimal pH range corresponds to the region
of minimum solubility (5.5 to 7.5 for alum and
from 5 to 8.5 for ferric salts).
• alum and ferric salts are strong acids. If the
alkalinity is too low, addition of a high alum dose
may drive the pH lower than the optimal range,
and a base may need to be added.
• Alternatively, water with high alkalinity may
require acid in addition the coagulant to lower
the pH into the optimal range.
Impact of Temperature
• Temperature affects the solubility constants for
the precipitation reactions and density of water.
• Cold water is more dense than warm water,
when the water temperature is near 4◦C, the
density of alum floc is very close to the density of
water.
• The floc may not settle well. Ferric hydroxide floc
is more dense than alum floc and can be a better
option in locations with very cold water.
Impact of NOM on coagulation
• NOM reacts or binds with metal ion coagulants,
• Qualitatively, as pH increases, humic substances
become more ionized and the positive charge on
metal coagulants will decrease.
• Higher coagulant dosages will be required at
higher pH values.
Polyelectrolytes / Organic polymers
• have two principal uses in water treatment:
• (1) as a coagulant for the destabilization of particles
• (2) as a filter aid to promote the formation of larger and
more shear-resistant flocs.
• polymers can be used to form a bridge between particles.
• Organic polymers are not generally used as primary
coagulants, they are often used after the particles have
been destabilised with metal coagulants.
• The main advantage of the combined usage is that the
dosage of metallic ion coagulants can be reduced by 40 to
80 percent.
• The lower metallic ion coagulant dosage in turn reduces
sludge and alkalinity consumption.
Enhanced coagulation
• Disinfection by-products (DBPs) are formed as a
result of chemical reactions between chlorine and
NOM
• Regulations in some countries include a
treatment technique that requires the removal of
NOM prior to disinfection.
• Performing coagulation for the purpose of
achieving specified removal of DBP precursors
(NOM) is known as enhanced coagulation.
Jar Testing for Coagulant Evaluation
• The selection of coagulants and dosage is determined
empirically using bench-scale and pilot-scale studies.
• Jar testing permits rapid evaluation of a range of
coagulant types and doses.
• The purpose of the jar test is to simulate the expected
or desired conditions in the coagulation–flocculation
facilities.
• The important factors that need to be evaluated in
jars and full-scale implementation are floc strength,
size, and settling rate
Jar test
• These parameters should be measured as part of the
jar test :
• (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 ultraviolet(UV) at 254 nm;
• (3) residual dissolved coagulant concentrations of Fe
or Al coagulants;
• (4) pH, and
• (5) alkalinity.
Jar test apparatus.

Square-shaped jars are used to avoid vortex flow, which

can occur if circular beakers are used.
 The Jar Test
• 6 beakers are filled with the raw
water, and then each is mixed
and flocculated uniformly by
identical paddle stirrers driven by
a single motor
• First dose each jar with the same
alum dose and vary the pH in
each jar.
• Repeat the test in a second set of
jars by holding the pH constant at
the optimum pH and varying the
coagulant dose.
Jar Test
• the test consists of a rapid-mix phase with simple
batch addition of the coagulant or coagulants
followed by a slow-mix period to simulate
flocculation.
• Flocs are allowed to settle and samples are taken
from the supernatant.
Example Jar Test
• The objective is to find the optimal pH, coagulant
dose, and the theoretical amount of alkalinity that
would be consumed at the optimal dose.
• Two sets of such jar tests were conducted on a
raw water containing 15 NTU and a HCO3-
alkalinity concentration of 50 mg/L expressed as
CaCO3 .
• The turbidity was measured after the mixture was
allowed to settle for 30 minutes.
Coagulant Aids
• Insoluble particulate materials such as clay,
sodium silicate, pure precipitated calcium
carbonate, and activated carbon have been used
as coagulant aids.
• They are used in waters that have low
concentrations of particles and, thus, have few
nucleating sites to form larger floc. Because their
density is higher than most floc particles, floc
settling velocity is increased by the addition of
coagulant aids. The dosage must be carefully
controlled to avoid lowering the water quality.
Factors to be considered in Coagulant Selection
• High turbidity, high alkalinity water is the easiest
to coagulate. Control of the pH is of utmost
importance in coagulating high turbidity, low
alkalinity water.
• Addition of a base may be required for alum and
ferric chloride.
• Low turbidity, low alkalinity waters are the most
difficult to coagulate. pH adjustment is required.
Direct filtration should be considered for this type
of water.
Practical Design Issues
• For the design of coagulation and flocculation
facilities, engineers must consider four process issues:
• (1) the type and concentration of coagulants and
flocculant aids,
• (2) the mixing intensity and the method used to
disperse chemicals into the water for destabilization,
• (3) the mixing intensity and time for flocculation,
• (4) the selection of the liquid–solid separation process
(e.g., sedimentation and filtration)
Mixing
• The rapid initial mixing of the metal salts in water
treatment is extremely important.
• achieving extremely low mixing times in large
treatment plants is often difficult, low mixing
times can be achieved by using multiple mixers.
• Recommend mixing times of less than 1 s.
• For sweep flow coagulation with aluminum
hydroxide precipitate, short times are not as
critical because the precipitate forms slower in
the range of 1 to 7s
Mixing
• Mixing is commonly referred to as flash mixing,
rapid mixing, or initial mixing.

• The purpose of rapid mixing is to provide a

uniform dispersion of coagulant chemical
throughout the influent water.
• Several points of addition for coagulant chemicals
should be provided in the rapid mixing and
flocculation processes.
• Oxidation with air and chemical oxidants such as
chlorine and potassium permanganate may also aid
coagulation by oxidizing iron and manganese, which
can aid floc formation.
• Carbon addition, typically in the form of powdered
activated carbon (PAC), may also improve coagulation,
as it removes organic matter prior to coagulation.
• Coagulation is performed in a rapid-mix unit that
is designed to bring together the coagulant and
particles in an efficient manner.
• Flocculation is performed in basins that are
designed to bring the particles in contact with one
another and form larger particles that can be
removed by gravity separation or filtration.
Flocculation
• The objective of flocculation is to bring the particles
into contact so that they will collide, stick together,
and grow to a size that will readily settle or filter out.
• Enough mixing must be provided to bring the floc into
contact and to keep the floc from settling in the
flocculation basin. Too much mixing will shear the floc
particles so that the floc is small and finely dispersed.
Therefore, the velocity gradient must be controlled
within a relatively narrow range.
• Flocculation is the most important factor affecting
particle-removal efficiency.
Flocculation
• Two general types of flocculation can be identified:
• (1) micro-flocculation (also known as perikinetic
flocculation) in which particle aggregation is brought about
by the random thermal motion of fluid molecules (known
as Brownian motion,
• (2) macro-flocculation (also known as orthokinetic
flocculation) particle aggregation is brought about by
inducing velocity gradients and gentle mixing in the fluid
containing the particles.
• or macro-flocculation by differential settling in which large
particles overtake small particles to form larger particles.
• Mixing for flocculation generally lasts for 20 to 40 min.
Principles of Flocculation
• Flocculation theories have evolved from the following
observations:
• (1) small particles undergo random Brownian motion
due to collisions with fluid molecules resulting in
particle–particle collisions
• (2) stirring water containing particles creates velocity
gradients that bring about particle collisions.
• (3) differential settling in which large particles settling
in a quiescent basin overtake small particles to form
larger particles.
 Particles Flocculate by Three Mechanisms

Differential
Fluid Shear: Sedimentation:
Brownian Motion: Particles Collide by Particles Collide
Particles Collide Traveling on Due to Different
Due to Random Different Terminal Velocities
Motion Streamlines at
Different Velocities
Macroscale Flocculation
• Mixing is the major flocculation mechanism for
particles greater than 1μ m in diameter.
• Mechanical mixing is employed to achieve
orthokinetic flocculation.
• Mechanical mixing causes unequal shearing
forces on the floc, and some of the floc are
broken up.
Principles of Mixing for Coagulation and
Flocculation: Velocity Gradient
• Camp and Stein (1943) proposed that the velocity
gradient averaged over the entire basin, the
global root-mean-square (RMS) velocity gradient,
might serve as a useful design parameter for
flocculation facilities.
Velocity Gradients
• For rapid-mix units, very high velocity gradients
are required (e.g., G = 600 − 5000 s−1),
• flocculation requires a velocity gradient high
enough to contact the particles to allow them to
flocculate without settling out of solution and yet
low enough to prevent particles from falling apart
due to shear forces caused by mixing (e.g., G = 20
− 50 s−1).
Mixing Theory
• The velocity gradient may be thought of as the amount of
shear taking place; that is, 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. The RMS velocity gradient may be
estimated as
𝑃 1 2
•𝐺 =
∀𝜇
• where G = global RMS velocity gradient, s-1
• P = power of mixing input to vessel, W
• μ = dynamic viscosity of water, Pa.s
• ∀ = volume of liquid, m3
Mixing theory
• 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 from tearing apart.
Time requirements for flocculation
• The time requirements for flocculation depend on the
requirements of downstream processes.
• For conventional treatment (settling follows flocculation) the
flocculation time ranges from 20 to 30 minutes.
• If direct filtration is to follow flocculation, shorter times on the
order of 10 to 20 minutes are often selected.
• In ideal reactors the average time in the reactor (the theoretical
detention time is defined as
∀
•𝑡=
𝑄
• 𝑡 = 𝑡ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑑𝑒𝑡𝑒𝑛𝑡𝑖𝑜𝑛 𝑡𝑖𝑚𝑒, 𝑠,
• ∀ = 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑓𝑙𝑢𝑖𝑑 𝑖𝑛 𝑟𝑒𝑎𝑐𝑡𝑜𝑟. 𝑚3,
• 𝑄 = 𝑓𝑙𝑜𝑤 𝑟𝑎𝑡𝑒, 𝑚3/𝑠
Selection of G and Gt Values
• Both G and the product of the velocity gradient and time ( Gt ),
serve as criteria for the design of mixing systems.
• Jar test data may be used to identify whether adsorption
/destabilization or sweep coagulation is predominant using the
following procedure:
• Determine the optimum pH and dose from plots of settled
turbidity
• Plot the optimum pH and dose.
• Determine which is the predominant mechanism from the
plotted position.
• G values in the range of 3,000 to 5,000 s -1 and detention times
on the order of 0.5 s are recommended for
adsorption/destabilization reactions. For sweep coagulation,
detention times of 1 to 10 s and G values in the range of 600 to
1,000 s -1 are recommended