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TITLE : COAGULATION AND FLOCCULATION

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OBJECTIVES
At the end of this experiment students should be able :
i)

To understand the coagulation and flocculation process in wastewater
treatment

ii)

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To remove turbidity from wastewater.

THEORY

In wastewater treatment system, the processes of coagulation and flocculation
are employed to separate suspended solids from water. Although the terms
coagulations and flocculation are often used interchangeably, or the single term
“flocculations” is used to describe both; they are, in fact, two distinct processes.
Knowing their differences can lead to a better understanding of the clarification
and dewatering of wastewater treatment.

Finely dispersed solids (colloids) suspended in wastewaters are stabilized by
negative electric charges on their surfaces,causing them to repel each other. To
assist in the removal of colloidal particles from suspension, chemical coagulation
and flocculation are required. These processes are combination of physical and
chemical procedures and usually done in sequence. Chemicals are mixed with
wastewater to promote the aggregation of the suspended solids into particles
large enough to settle or be removed.

Coagulation is the destabilization of colloids by neutralizing the forces that keep
them apart. Cationic coagulants provide positive electric charges to reduce the
negative charge of the colloids. As a results, the particles collide to form large

particles(flocs). Rapid mixing is required to disperse the coagulant throughout the
liquid.

Flocculation is a water treatment process following coagulations, which uses
gentle stirring to bring the suspended particles together so they will form larger,
more settleable clumps called floc.

Once suspended particles are flocculated into larger particles , they can usually
be removed from the liquid by sedimentation, provided that a sufficient density
difference exists between the suspended matter and the liquid. Such particles
can also be removed or separated by media filtration, straining or floatation.
When a filtering process is used, the addition of a flocculant may not be required
since the particles formed by the coagulation reaction may be sufficient size to
allow removal. The flocculation reaction not only increases the size of the floc
particles to settle them faster, but also affects the physical nature of the floc,
making these particles less gelatinous and thereby easier to dewater.

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APPARATUS/EQUIPMENT

i)

Glass rod

ii)

Beaker

iii)

Wastewater sample

iv)

Poly aluminium chloride ( PAC )

v)

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Aluminium sulphate ( alum )

WORKSHOP RULES AND REGULATIONS
1) Conduct yourself in a responsible manner at all times in the laboratory
2) Follow all written and verbal instructions carefully. If your do not understand a direction
or part of a procedure, ask your instructor before proceeding with the activity.
3) Never work alone in the laboratory. No student may work in the laboratory without the
presence of the instructors.
4) When first interring a laboratory, do not touch any equipment, chemicals, or other
materials in the laboratory area until you are instructed to do so.
5) Perform only those experiments authorized by your instructor. Carefully follow all
instructions, both written and oral. Unauthorized experiments are not allowed.
6) Do not eat food, drink beverages, or chew gum in the laboratory. Do not use laboratory
glassware as containers for food or beverages.
7) Be prepared for your work in the laboratory. Read all procedures thorougly before
entering the laboratory. Never fool around in the laboratory. Horseplay, practical jokes,
and pranks are dangerous and prohibited.
8) Be alert and proceed with caution at all time sin the laboratory. Notify the instructor
immediately of any unsafe conditions you observe.
9) Experiments must be personally monitored at all times. Do not wonder around the room,
distract other students, startle other students or interface with the laboratory experiments
of others.
10) Report any accident or injury to the lecturer or instructor.

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DISCUSSION

1) a. COAGULATION
The first step destabilizes the particle’s charges. Coagulants with charges opposite those of the
suspended solids are added to the water to neutralize the negative charges on dispersed nonsettable solids such as clay and color-producing organic substances.
Once the charge is neutralized, the small suspended particles are capable of sticking together.
The slightly larger particles formed through this process and called microflocs, are not visible to
the naked eye. The water surrounding the newly formed microflocs should be clear. If it is not,
all the particles’ charges have not been neutralized, and coagulation has not been carried to
completion. More coagulant may need to be added.
A high-energy, rapid-mix to properly disperse the coagulant and promote particle collisions is
needed to achieve good coagulation. Over-mixing does not affect coagulation, but insufficient
mixing will leave this step incomplete. Coagulants should be added where sufficient mixing will
occur. Proper contact time in the rapid-mix chamber is typically 1 to 3 minutes.
The commonly used metal coagulants fall into two general categories: those based on aluminum
and those based on iron. The aluminum coagulants include aluminum sulfate, aluminum chloride
and sodium aluminate. The iron coagulants include ferric sulfate, ferrous sulfate, ferric chloride
and ferric chloride sulfate. Other chemicals used as coagulants include hydrated lime and
magnesium carbonate.
The effectiveness of aluminum and iron coagulants arises principally from their ability to form
multi-charged polynuclear complexes with enhanced adsorption characteristics. The nature of the
complexes formed may be controlled by the pH of the system.
When metal coagulants are added to water the metal ions (Al and Fe) hydrolyze rapidly but in a
somewhat uncontrolled manner, forming a series of metal hydrolysis species. The efficiency of
rapid mixing, the pH, and the coagulant dosage determine which hydrolysis species is effective
for treatment.
There has been considerable development of pre-hydrolyzed inorganic coagulants, based on both
aluminum and iron to produce the correct hydrolysis species regardless of the process conditions
during treatment. These include aluminum chlorohydrate, polyaluminum chloride,
polyaluminum sulfate chloride, polyaluminum silicate chloride and forms of polyaluminum
chloride with organic polymers. Iron forms include polyferric sulfate and ferric salts with
polymers. There are also polymerized aluminum-iron blends.
The principal advantages of pre-polymerized inorganic coagulants are that they are able to
function efficiently over wide ranges of pH and raw water temperatures. They are less sensitive
to low water temperatures; lower dosages are required to achieve water treatment goals; less

chemical residuals are produced; and lower chloride or sulfate residuals are produced, resulting
in lower final water TDS. They also produce lower metal residuals.
Pre-polymerized inorganic coagulants are prepared with varying basicity ratios, base
concentrations, base addition rates, initial metal concentrations, ageing time, and ageing
temperature. Because of the highly specific nature of these products, the best formulation for a
particular water is case specific, and needs to be determined by jar testing. For example, in some
applications alum may outperform some of the polyaluminum chloride formulations.
Important mechanisms relating to polymers during treatment include electrostatic and bridging
effects. Figure 1 shows schematic stages in the bridging mechanism. Polymers are available in
various forms including solutions, powders or beads, oil or water-based emulsions, and the
Mannich types. The polymer charge density influences the configuration in solution: for a given
molecular weight, increasing charge density stretches the polymer chains through increasing
electrostatic repulsion between charged units, thereby increasing the viscosity of the polymer
solution.

b. FLOCCULATION
i) Definition
Flocculation, in the field of chemistry, is a process wherein colloids come out of suspension in
the form of floc or flake; either spontaneously or due to the addition of a clarifying agent. The
action differs from precipitation in that, prior to flocculation, colloids are merely suspended in a
liquid and not actually dissolved in a solution. In the flocculated system, there is no formation of
a cake, since all the flocs are in the suspension.

ii) Purpose
Following the first step of coagulation, a second process called flocculation occurs. Flocculation,
a gentle mixing stage, increases the particle size from submicroscopic microfloc to visible
suspended particles.
The microflocs are brought into contact with each other through the process of slow mixing.
Collisions of the microfloc particles cause them to bond to produce larger, visible flocs called
pinflocs. The floc size continues to build through additional collisions and interaction with
inorganic polymers formed by the coagulant or with organic polymers added. Macroflocs are
formed. High molecular weight polymers, called coagulant aids, may be added during this step to
help bridge, bind, and strengthen the floc, add weight, and increase settling rate. Once the floc
has reached it optimum size and strength, the water is ready for the sedimentation process.
Design contact times for flocculation range from 15 or 20 minutes to an hour or more.
The purpose of Flocculation is to promote the interaction of particles and
form aggregates that can be efficiently removed during sedimentation and filtration. This
document describes how this process should function.

2) What is turbidity?
i) Definition
Turbidity is a cloudy appearance of water caused by small particles suspended therein. Water
with little or no turbidity will be clear. Turbidity is the cloudiness or haziness of a fluid caused
by individual particles (suspended solids) that are generally invisible to the naked eye, similar to
smoke in air. The measurement of turbidity is a key test of water quality.

Fluids can contain suspended solid matter consisting of particles of many different sizes. While
some suspended material will be large enough and heavy enough to settle rapidly to the bottom
of the container if a liquid sample is left to stand (the settable solids), very small particles will
settle only very slowly or not at all if the sample is regularly agitated or the particles
are colloidal. These small solid particles cause the liquid to appear turbid.
Turbidity (or haze) is also applied to transparent solids such as glass or plastic. In plastic
production haze is defined as the percentage of light that is deflected more than 2.5° from the
incoming light direction.

ii) Cause
Turbidity in open water may be caused by growth of phytoplankton. Human activities that
disturb land, such as construction, mining and agriculture, can lead to high sediment levels
entering water bodies during rain storms due to storm water runoff. Areas prone to high bank
erosion rates as well as urbanized areas also contribute large amounts of turbidity to nearby
waters, through storm water pollution from paved surfaces such as roads, bridges and parking
lots. Certain industries such as quarrying, mining and coal recovery can generate very high levels
of turbidity from colloidal rock particles.
In drinking water, the higher the turbidity level, the higher the risk that people may develop
gastrointestinal. This is especially problematic for immunocompromised people, because
contaminants like viruses or bacteria can become attached to the suspended solid. The suspended
solids interfere with water disinfection with chlorine because the particles act as shields for the
virus and bacteria. Similarly, suspended solids can protect bacteria from ultraviolet (UV)
sterilization of water.
In water bodies such as lakes, rivers and reservoirs, high turbidity levels can reduce the amount
of light reaching lower depths, which can inhibit growth of submerged plant sand consequently
affect species which are dependent on them, such as fish and shellfish. High turbidity levels can
also affect the ability of fish gills to absorb dissolved oxygen. This phenomenon has been
regularly observed throughout the Chesapeake Bay in the eastern United.

For many mangrove areas, high turbidity is needed to support certain species, such as to protect
juvenile fish from predators. For most mangroves along the eastern coast of Australia, in
particular Moreton Bay, turbidity levels as high as 600 Nephelometric Turbidity Units (NTU) are
needed for proper ecosystem.

iii) Measurement
The most widely used measurement unit for turbidity is the FTU (Formazin Turbidity Unit). ISO
refers to its units as FNU (Formazin Nephelometric Units).
There are several practical ways of checking water quality, the most direct being some measure
ofattenuation (that is, reduction in strength) of light as it passes through a sample column of
water. The alternatively used Jackson Candle method (units: Jackson Turbidity Unit or JTU) is
essentially the inverse measure of the length of a column of water needed to completely obscure
a candle flame viewed through it. The more water needed (the longer the water column), the
clearer the water. Of course water alone produces some attenuation, and any substances
dissolved in the water that produce color can attenuate some wavelengths. Modern instruments
do not use candles, but this approach of attenuation of a light beam through a column of water
should be calibrated and reported in JTUs.
A property of the particles—that they will scatter a light beam focused on them—is considered a
more meaningful measure of turbidity in water. Turbidity measured this way uses an instrument
called a nephelometer with the detector setup to the side of the light beam. More light reaches the
detector if there are lots of small particles scattering the source beam than if there are few. The
units of turbidity from a calibrated nephelometer are called Nephelometric Turbidity Units
(NTU). To some extent, how much light reflects for a given amount of particulates is dependent
upon properties of the particles like their shape, color, and reflectivity. For this reason (and the
reason that heavier particles settle quickly and do not contribute to a turbidity reading), a
correlation between turbidity and total suspended solids(TSS) is somewhat unique for each
location or situation.
Turbidity in lakes, reservoirs, channels, and the ocean can be measured using a Secchi disk. This
black and white disk is lowered into the water until it can no longer be seen; the depth (Secchi
depth) is then recorded as a measure of the transparency of the water (inversely related to
turbidity). The Secchi disk has the advantages of integrating turbidity over depth (where variable
turbidity layers are present), being quick and easy to use, and inexpensive. It can provide a rough
indication of the depth of the euphotic zone with a 3-fold division of the Secchi depth, however
this cannot be used in shallow waters where the disk can still be seen on the bottom.
An additional device, which may help measuring turbidity in shallow waters is the Turbidity
tube. The Turbidity tube condenses water in a graded tube which allows determination of
turbidity based on a contrast disk in its bottom, being analog to the Secchi disk.

Turbidity in air, which causes solar attenuation, is used as a measure of pollution. To model the
attenuation of beam irradiance, several turbidity parameters have been introduced, including the
Linke turbidity factor.

iV) Treatment
Turbidity is commonly treated using either a settling or filtration process. Depending on the
application, chemical reagents, will be dosed into the wastewater stream to increase the
effectiveness of the settling or filtration process. Potable water treatment and municipal
wastewater plants often remove turbidity with a combination of sand filtration, settling tanks and
clarifiers.
In-situ water treatment or direct dosing for the treatment of turbidity is common when the
affected water bodies are dispersed (i.e. there are numerous water bodies spread out over a
geographical area, such as small drinking water reservoirs), when the problem is not consistent
(i.e. when there is turbidity in a water body only during and after the wet season) or when a low
cost solution is required. In-situ treatment of turbidity involves the addition of a reagent,
generally a flocculants, evenly dispensed over the surface of the body of water. The flocs then
settle at the bottom of the water body where they remain or are removed when the water body is
drained. This method is commonly used at coal mines and coal loading facilities where storm
water collection ponds have seasonal issues with turbidity. A number of companies offer
portable treatment systems for in-situ water treatment or direct dosing of reagents.

3) What is the purpose of adding PAC and alum into wastewater sample?
i) POLYALUMINUM CHLORIDE (PAC)
Use of clay in water and wastewater treatment has been investigated by many research studies;
found that addition of Bentonite to raw water performed effectively at temperature 20-37C and
pH < 8. used Bentonite as absorbent material for treating municipal wastewater, and they found
that COD decreased to < 20mg/L. reported that organic particles can be absorbed by clay
minerals and therefore clays can be used for wastewater treatment. Investigated the effect of
clay as coagulant aid with alum in industrial wastewater of paper, and they found that the
combined use of clay and alum is more efficient in colour removal than using alum alone.
Reported that Bentonite can perform effectively at removing certain cationic components from
wastewater and it can be used for treating waters containing heavy color and low turbidity.
Recently proved that ruwage performed efficiently at different levels of turbidity and wide range
of pH (3-10). On the other hand chemical coagulants are intensively and increasingly used at
wastewater treatments plants, among which is Ploy Aluminum Chloride (PAC), which is
characterized by various advantages such as working in wide range of pH and low temperatures

and significant efficiency at low concentrations comparing to other conventional coagulants
based on Al- or Fe(III) chlorides and sulfates. The huge discharge of industrial, municipal and
drainage wastewater from cities, factories and agricultural schemes in Sudan into river Nile and
its tributaries with limited or no treatments in addition to the cost of the chemical coagulants are
representing the main environmental challenges facing the country. To provide a possible
solution, this study was conducted to investigate the effect of two clay soils as abundant natural
coagulants and their combination with PAC to remove turbidity, COD, and color from
wastewater, which will minimize the treatment cost.
Composition: The term "poly-aluminum chloride" or "PAC" refers to a class of soluble
aluminum products in which aluminum chloride has been partly reacted with base. The relative
amount of OH-, compared to the amount of Al, determines the basicity of a particular PAC
product. The chemistry of PAC is often expressed in the form Aln(OH)mCl(3n-m). Basicity can
be defined by the term m/(3n) in that equation. Because PAC is more expensive to produce than
papermakers alum (aluminum sulfate) it is important to note the most important differences
between these two products. Solutions of PAC are not as acidic as alum; consequently they do
not tend to decrease the pH of the furnish nearly as much as an equivalent amount of alum.
Another difference is that PAC is formulated so that it already contains some of the highly
cationic oligomers of aluminum - materials that are especially effective for the modification of
colloidal charges in a papermaking furnish. A particularly stable and important ionic species in
PAC and related soluble aluminum chemicals has the formula Al12(OH)24AlO4(H2O)127+.
Function: To boost drainage rates especially in neutral and alkaline papermaking, to help with
certain retention aid strategies, and for neutral sizing with certain rosin-based emulsion products.
PAC products of low (0 to 17%) and medium (17 to 50%) are commonly used in papermaking
applications, whereas PAC products of higher basicity are useful for water and wastewater
treatment.
Strategies for Use: Because PAC is less acidic than alum there is less danger of shocking the
system with a pH change at the point of addition. That means that papermakers have a certain
degree of flexibility regarding the point of addition. An example worth considering is the case of
virgin unbleached linerboard, when it is made under acidic papermaking conditions. The pulp
often contains a significant level of barium compounds. Addition of alum depresses the pH,
converting Ba(OH)2 to soluble divalent barium. The barium ions build up in the system until the
solution is supersaturated with respect to barium sulfate. Insoluble, hard, barium sulfate scale
then precipitates from solution onto solid surfaces exposed to high levels of shear. Substitution
of PAC for alum in such cases can reduce the problem considerably by decreasing the amount of
pH drop and avoiding an additional contribution of sulfate ions. One has always to be careful of
the dosage of PAC, since an overdose is expected to convert the net colloidal charge of the
system to a positive sign. In the presence of calcium carbonate filler, the use of PAC in place of
alum is likely to reduce the amount of dissolution of the calcium carbonates.

ii) Alum
Alum is both a specific chemical compound and a class of chemical compounds. The specific
compound is the hydrated potassiumaluminium sulfate (potassium alum) with
the formula KAl(SO4)2·12H2O. More widely, alums are double sulphate salts, with the formula
AM(SO4)2·12H2O, where A is a monovalent cation such as potassium or ammonium and M is
a trivalent metal ion such as aluminium or chromium(III).
Potassium alum is the common alum of commerce, although soda alum, ferric alum,
and ammonium alum are manufactured.
Alum has been used at least since Roman times for purification of industrial process water.
Between 30 and 40 ppm of alum for household wastewater, often more for industrial
wastewater, is added to the water so that the negatively charged colloidal particles clump
together into "flocs", which then float to the top of the liquid, settle to the bottom of the liquid, or
can be more easily filtered from the liquid, prior to further filtration and disinfection of the water.
Aluminium sulfate is used in water purification and as a mordant in dyeing and printing textiles.
In water purification, it causes impurities to coagulate which are removed as the particulate
settles to the bottom of the container or more easily filtered. This process is
called coagulation or flocculation.
When dissolved in a large amount of neutral or slightly alkaline water, aluminium sulfate
produces a gelatinous precipitate of aluminium hydroxide, Al(OH)3. In dyeing and printing cloth,
the gelatinous precipitate helps the dye adhere to the clothing fibers by rendering the pigment
insoluble.
The addition of alum (hydrated aluminum sulfate) to a wastewater produces the hydrolysis of the
sulfate with the consequent formation of insoluble aluminum hydroxide according to the
reactions.
The insoluble aluminum hydroxide forms a floc precipitate responsible for colloid removal.
Note that if the wastewater is not buffered the resulting H+ generation (pH increase) will prevent
the reaction from proceeding any further.

4) What are the factors which influence coagulation and flocculation process?
In a well-run water treatment plant, adjustments are often necessary in order to maximize the
coagulation/flocculation process. These adjustments are a reaction to changes in the raw water
entering the plant. Coagulation will be affected by changes in the water's pH, alkalinity,
temperature, time, velocity and zeta potential.
The effectiveness of a coagulant is generally pH dependent. Water with a color will coagulate
better at low pH (4.4-6) with alum.
Alkalinity is needed to provide anions, such as (OH) for forming insoluble compounds to
precipitate them out. It could be naturally present in the water or needed to be added as
hydroxides, carbonates, or bicarbonates. Generally 1 part alum uses 0.5 parts alkalinity for
proper coagulation.
The higher the temperature, the faster the reaction, and the more effective is the coagulation.
Winter temperature will slow down the reaction rate, which can be helped by an extended
detention time. Mostly, it is naturally provided due to lower water demand in winter.
Time is an important factor as well. Proper mixing and detention times are very important to
coagulation.
The higher velocity causes the shearing or breaking of floc particles, and lower velocity will let
them settle in the flocculation basins. Velocity around 1 ft/sec in the flocculation basins should
be maintained.
Zeta potential is the charge at the boundary of the colloidal turbidity particle and the surrounding
water. The higher the charge the more is the repulsion between the turbidity particles, less the
coagulation, and vice versa. Higher zeta potential requires the higher coagulant dose. An
effective coagulation is aimed at reducing zeta potential charge to almost 0.
The proper type and concentration of coagulant are essential to the coagulation process. The
coagulant choice will depend on the conditions at the plant. The concentration of coagulant also
depends on the water conditions, and a jar test can be used to determine the correct concentration
to use at any given time.
Coagulants are usually fed into the water using a gravimetric feeder or a metering pump.
A gravimetric feeder feeds dry chemicals into the water by weight. A metering pump feeds a
wet solution (a liquid) into the water by pumping a volume of solution with each stroke or
rotation.

Improper coagulation related to coagulant may result from:


Using old chemicals
Using the wrong coagulant
Using the wrong concentration of coagulant. This may result from setting the wrong feed
rate on the gravimetric feeder or metering pump or from a malfunction of the equipment.

Coagulation/flocculation is a process used to remove turbidity, color, and some bacteria from
water. In the flash mix chamber, chemicals are added to the water and mixed violently for less
than a minute. These coagulants consist of primary coagulants and/or coagulant aids. Then, in
the flocculation basin, the water is gently stirred for 30 to 45 minutes to give the chemicals time
to act and to promote floc formation. The floc then settles out in the sedimentation basin.
Coagulation removes colloids and suspended solids from the water. These particles have a
negative charge, so the positively charged coagulant chemicals neutralize them during
coagulation. Then, during flocculation, the particles are drawn together by van der Waal's
forces, forming floc. The coagulation/flocculation process is affected by pH, salts, alkalinity,
turbidity, temperature, mixing, and coagulant chemicals.

REFERENCE
1) Coagulation and Flocculation Process Fundamentals
www.mrwa.com/OP-Coagulation.pdf
2) Flocculation - Wikipedia, the free encyclopedia
en.wikipedia.org/wiki/Flocculation
3) Turbidity - Wikipedia, the free encyclopedia
http://en.wikipedia.org/wiki/Turbidity