Unit Operations in

Water and Wastewater Treatment:

Coagulation and Flocculation

EnE 203 Introduction to Environmental Engineering

Lecture 6.1

Analiza P. Rollon, Ph.D.

Professor
Department of Chemical Engineering
College of Engineering
University of the Philippines
 Contents

Overview on Coagulation and flocculation

principle, application, design considerations
 Coagulation & Flocculation
• Coagulation-flocculation is a chemical water treatment
technique typically applied prior to sedimentation and
filtration (e.g. rapid sand filtration) to enhance the ability of a
treatment process to remove particles.
• Coagulation is a process used to neutralize charges and form a
gelatinous mass to trap (or bridge) particles thus forming a
mass large enough to settle or be trapped in the filter.
• Flocculation is gentle stirring or agitation to encourage the
particles thus formed to agglomerate into masses large
enough to settle or be filtered from solution.
 Why coagulation and flocculation?

https://image.slidesharecdn.com/pptcoagulationandflocculation-160331111058/95/ppt-coagulation-and-flocculation-2-638.jpg?cb=1459422671
 What is coagulation?
• Coagulation is the destabilization of colloidal
suspended particles in water by adding chemicals
(coagulants) that neutralizes the negative charge of
the dispersed particles so that they can aggregate
and form larger flocs.
• Examples of coagulants:
– aluminum sulfate Al2(SO4)3.14H2O
– or ferric chloride Fe2Cl3
– Ferric sulfate Fe2(SO4)3
– Polyaluminum chloride (PAC) Al2(OH) 3Cl3
 Coagulation: How?
• Coagulation destabilises the particles’
charges.
• Neutralization of charge: Coagulants with
charges opposite to those of the
suspended solids are added to the water to
neutralize the negative charges on
dispersed non-settable solids such as clay
and organic substances.
• Contact and adhesion: Once the charge is
neutralized, the small-suspended particles
are capable of sticking together. The
slightly larger particles formed through this
process are called microflocs and are still
too small to be visible to the naked eye.
 Mixing
• A high-energy, rapid-mix to properly disperse the coagulant
and promote particle collisions is needed to achieve good
coagulation and formation of the microflocs.
• Over-mixing does not affect coagulation, but insufficient
mixing will leave this step incomplete.
• Proper contact time in the rapid-mix chamber is typically 1 to
3 minutes.
Mixing
• Forces acting between
particles: repulsion due
to charge & attraction
due to van der Waals
 Flocculation
• Following coagulation,
flocculation, a gentle mixing stage,
increases the particle size from
submicroscopic microflocs to
visible suspended particles.
• The microflocs are brought into
contact with each other through
the process of slow mixing.
Collisions of the microflocs
particles cause them to bond to
produce larger, visible flocs.
• The floc size continues to build
through additional collisions and
interaction with inorganic
polymers formed by the coagulant
or with organic polymers added.
Coagulation-Flocculation-Sedimentation

• 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.
 Coagulation-Flocculation-Separation
• Once the floc has reached its optimum size and strength, the water is ready for
the separation process (sedimentation, floatation or filtration).
• Design contact times for flocculation range from 15 or 20 minutes to an hour
or more.
 Reagents
• The common reagents are:
– mineral and/or organic coagulants (typically iron and
aluminium salt, organic polymers),
– flocculation additives (activated silica, talcum, activated
carbon…),
– anionic or cationic flocculants, and
– pH control reagents such as acids or bases.
– Certain heavy metal chelating agents can also be added
during the coagulation step.
– Long carbon chain with active groups such as amine, N,
sulfate groups along the chain.
 How do we determine dosage of
coagulant?
Jar test
• to identify the most adapted mix of chemical compounds and
concentrations for coagulation-flocculation
• a batch test consisting of using several identical jars
containing the same volume and concentration of feed, which
are charged simultaneously with six different doses of a
potentially effective coagulant
• The six jars can be stirred simultaneously at known speeds.
The treated feed samples are mixed rapidly and then slowly
and then allowed to settle.  rapid mix, coagulation
flocculation and settling basins
 How do we determine dosage of
coagulant?
Jar test
• At the end of the settling period, test samples are drawn from
the jars and turbidity of supernatant liquid is measured.
• A plot of turbidity against coagulant dose gives an indication
of the optimum dosage (i.e. the minimum amount required to
give acceptable clarification).
• The criteria thus obtained from a bench jar test are
– the quality of resultant floc and
– the clarity of the supernatant liquid after settling.
 Jar Test: Determine Optimum pH
• Fill jars each with 500 – 1000 ml water
(usually 6 jars)
• Adjust pH of each to 5.0, 5.5, 6, 6.5, 7,
7.5 by adding H2SO4 or NaOH while
mixing.
• To each jar, add same dose of coagulant
(5 or 10 mg/L)
• Rapid mix (100 – 150 rpm) for 1 minute
to disperse the coagulant.
• Slow down mixing to 25-30 rpm and
continue mixing for 15-20 minutes (to
allow floc/larger particle formation)
• Stop mixing. Settle for 30-45 minutes.
• Measure final residual turbidity. Plot
residual turbidity vs. pH
 Jar Test: Determine Optimum pH
• The pH that
results in the
lowest residual
turbidity is the
optimum pH.
 Jar Test: Determine Optimum
Coagulant Dosage
• Fill jars each with 500 – 1000 ml water
(usually 6 jars)
• Adjust pH of each to the optimum pH
by adding H2SO4 or NaOH while mixing.
• Add different dose of coagulant (5, 7,
10, 12, 15, 20 mg/L)
• Rapid mix (100 – 150 rpm) for 1 minute
to disperse the coagulant.
• Slow down mixing to 25-30 rpm and
continue mixing for 15-20 minutes (to
allow floc/larger particle formation)
• Stop mixing. Settle for 30-45 minutes.
• Measure final residual turbidity. Plot
residual turbidity vs. coagulant dose.
 Jar Test: Determine Optimum
Coagulant Dosage
Example
(alum as coagulant)
• The coagulant dose
that results in the
lowest residual
turbidity is the
optimum dose.
 Application
• to separate the suspended and dissolved
compounds (turbidity) from the water in centralized
drinking water treatment plants
• To remove charged substances such as suspended
mineral, organics, pathogens, and dissolved species
such as metal ions, phosphates, fluoride, and
radionuclides can be separated by these processes.
• to remove suspended solids in domestic and
industrial wastewater treatment plants
Removal of Natural Organic Matter
• Natural organic material (NOM) is usually associated with
humic substances arising from the aqueous extraction of
living woody substances, the solution of degradation products
in decaying wood and the solution of soil organic matter.
• These substances are objectionable:
– impart color to waters
– act as a vehicle for transporting toxic substances and
micro-pollutants, including heavy metals and organic
pollutants;
– react with chlorine to form potentially carcinogenic by-
products.
Removal of Natural Organic Matter
• The degree to which coagulation can remove organic material
depends on the type of material present.
• The specific ultraviolet absorption (SUVA) is related to the
concentration and type of dissolved organic carbon (DOC)
present, as follows:
SUVA = UV254/DOC (l/mg m)
where:
UV254 is the ultraviolet absorbance measure at a wavelength of
253.7 nm, after filtration through 0.45-µm filters (m-1);
DOC is the dissolved organic carbon measured after filtration
through 0.45-µm filters (mg/l).
Removal of Natural Organic Matter

Influence of SUVA on alum (as Al) requirements for DOC removal

• In general, lower molecular weight species such as the fulvic

acids are more difficult to remove by coagulation. Higher
molecular weight humic acids tend to be easier to remove.
Removal of Natural Organic Matter
• Organics removal and enhanced coagulation are effective with
traditional coagulants like aluminum sulfate, ferric chloride
and ferric sulfate, as well as formulations like polyaluminum
chloride (PACl) and acid alum.
• Acid alum formulations are aluminum sulfate with 1 to 15-
percent free sulfuric acid. Their effectiveness with TOC
removal applications is due to the enhanced depression of pH.
• TOC or NOM reductions depend on the type and dosage of
coagulant, the pH, temperature, raw water quality and NOM
characteristics.
• In general, the optimum pH for ferric salts is in the range 3.7
to 4.2, and for aluminum sulfate in the range 5.0 to 5.5.
Removal of Natural Organic Matter
• In some cases, the removal of lower weight organics has been
improved by supplementing treatment with metal coagulants
with powdered activated carbon (PAC). In one case with raw
water TOC of 2.4 mg/l, a combination of an alum-polymer
blend coagulant at 25 mg/l with PAC at 10 mg/l was optimal
to achieve a 39-percent TOC reduction.
• In another case, a water with a low humic content and low
SUVA (1.43 l/mg.m) was treated with 65 mg/l FeCl3 and 23
mg/l PAC. Fifty-six percent of the TOC was non-humic and 46-
percent of the TOC had molecular weights less than 1,000.
 Removal of Pathogens
• Giardia removal or inactivation & at least 99-percent (2-log)
removal of Cryptosporidium.
• Adequately designed and operated water treatment plants,
with coagulation, flocculation, sedimentation & filtration: 2.5-
log removal for Giardia, leaving only 0.5-log inactivation to be
achieved by disinfection.
 Removal of Pathogens
• Coagulation and flocculation, with dissolved air flotation (DAF)
for clarification, has achieved average log removal
of Giardia and Cryptosporidium of 2.4 and 2.1, respectively.
• Optimum coagulation conditions were governed by turbidity
and NOM removal requirements, rather than by pathogen
removals.
• Overall Giardia and Cryptosporidium removal, including
the filtration step were approximately 5-log.
 Removal of Pathogens
• Cryptosporidium oocyst surfaces: probably of polysaccharide
layers but negative charge due to carboxylic end of surface
proteins.
• Removal of Cryptosporidium using alum coagulation: sweep
floc mechanism (not via charge neutralization mechanism at
lower DOC concentrations).
• At higher DOC: removal is mediated by a NOM-assisted
bridging between aluminum hydroxide and oocyst particles.
 Removal of Virus
• Up to 99.9% virus removal using metal coagulants (aluminum
and ferric salts) and polyelectrolytes (cationic).
• Disadvantage: if other material is present in the form of color,
turbidity, and COD, removal of such material is poor.
• Using metal coagulants and poyelectrolytes conjointly 
better floc characteristics
• variety of substances in water use of both metal coagulants
and polyelectrolytes will effect a higher overall removal
• depends on the conditions pertaining for each case.
• Polyelectrolytes as flocculant aids: floc formation improves
but does not appear to improve virus removals beyond those
achieved using metal coagulants alone.
 Removal of Virus
• Viruses are essentially DNA (deoxyribonucleic acid) or RNA
(ribonucleic acid) units contained within a protein coat.
• Destabilization mechanism: coordination reactions between
metal coagulant species and carboxyl groups of the virus coat
protein
• for organic color and viruses: optimum removals occur at similar
pH values.
• optimum pH for virus removal with aluminum sulfate: ca. 5.0
97.7 to 99.8% virus removal
• Using a cationic polyelectrolyte as flocculant aid, virus and
turbidity removals increases to 99.9 and 98.5% respectively.
 Removal of Virus
• Metal coagulants or polyelectrolytes do not fully inactivate
viruses.
• For a safe drinking water, disinfection of the water before
distribution is required.
• Some reports: infectious virus concentration only recovers
partially after re-dissolution of aluminum hydroxide
precipitates  virucidal activity of the aluminum.
• PACl coagulants: higher virucidal activity vs. alum.
• NOM in water inhibits virucidal activity of the aluminum.
 Removal of Inorganics: Arsenic
• Arsenic is stable in several oxidation states, under different
redox conditions in water.
• Groundwater: arsenite, As(III) and arsenate, As(V).
• In anaerobic conditions (oxygen-free): As(III) is predominant
form
• In aerobic waters: As(V) more common
• In general, As(V) is more readily removed than As(III).
 Removal of Inorganics: Arsenic
Arsenic removal:
– adsorption on granular iron based media;
– adsorption on ion exchange resins;
– adsorption on activated alumina;
– Co-precipitation in iron removal plants;
– coagulation with alum or ferric followed by
conventional filtration; and
– coagulation with ferric followed by membrane filtration.
• Some studies on arsenic removal: coagulation is more
economical than other treatment alternatives.
 Removal of Inorganics: Arsenic
• Iron coagulants are generally more effective than aluminum
coagulants.
• Iron coagulants added to water hydrolyze to form ferric
hydroxide with a net positive charge.
– This net positive charge is a function of pH.
– As the pH decreases, the number of positively charged sites on the
ferric hydroxide particles increases.
– Arsenate, As(V) is an anion and since it is negatively charged, it will
adsorb to the positively charged ferric hydroxide particles by surface
complexation.
• Optimum pH: < 7
 Removal of Inorganics: Arsenic
• Aluminum coagulants: efficiencies for arsenic(V) removal
 polyaluminum chloride > polyaluminum sulfate >
aluminum chloride > aluminum sulfate.
 Optimum pH: 5.5.
 Dosages of 0.8 to 1.9 mg/l as Al, with Sedimentation,
filtration: 59-99% Arsenic removal
• Iron coagulants: efficiencies for arsenic(V) removal
– polyferric chloride > polyferric sulfate > feric chloride >
ferric sulfate.
– Best results at pH 5.5
– dosages of 1.7 to 3.8 mg/l as Fe, + sedimentation,
filtration: 70-99.6% As(V) removal
 Removal of Fluoride
• EPA 1975, Drinking Water Standard: 1.4 - 2.4 mg/l fluoride 
prevent dental fluorosis and more serious effects.
• EPA 1985, benefits of fluoride for dental health vs. deleterious
effects  MCL of 4 mg/l, secondary MCL of 2 mg/l.
• Systems with fluoride levels between 2 mg/l and 4 mg/l must
provide the public with information about possible tooth
discoloration.
 Removal of Fluoride
• Fluoride removal:
– activated alumina adsorption and
– reverse osmosis.
• In some cases, aluminum coagulants are cost effective.
• Optimum pH: 6.0 to 7.5.
• Removal: adsorption of fluoride to aluminum hydroxide flocs
(at lower Al levels, aluminum-fluoride complexes remain in
solution).
– To reduce fluoride from 3.6 mg/l to 1.8 mg/l: Aluminum dosage 18
mg/l as Al or 10 mg Al per mg fluoride removed, at optimum pH 6.5.
– To further reduce the fluoride to 1.0 mg/l: 12 mg Al per mg fluoride
removed.
 Chemical Phosphorus Removal
• general relationship between effluent residual phosphorus
concentration and the ratio of metal added to P removed.
• Inordinate dosages, beyond stoichiometric, are required to
achieve very low effluent concentrations.
 Chemical Phosphorus Removal
• Within the stoichiometric range of phosphorus removal, there
is a tightening of the optimal pH range as the metal coagulant
dosage increases.
• Beyond the stoichiometric range, when final phosphorus
concentrations are progressively lower, the pH range widens
again, towards the side of higher pH.
• For example, with alum the optimum pH range for effluent P
concentrations down to approximately 0.2 is 5.5 to 6.0.
• As the Al ratio is increased for lower P concentrations, the
required pH range widens to 6.0 to 7.0.
 Chemical Phosphorus Removal
• Within the stoichiometric P removal range, a precipitation
model describes the interactions between metal and
phosphorus.
• At very low P concentrations, more complex models that
include precipitation, adsorption and floc specific surface are
required.

• sequential chemical addition for coagulation: For very low
final concentrations, overall coagulant dosages can be
significantly reduced.
 Chemical Phosphorus Removal
• The degree of phosphorus removal depends not only on the
coagulant added, but also on the mode of solid-liquid
separation employed.
• Effluent suspended solids contribute significantly to effluent
total phosphorus concentrations.
• For very low phosphorus residuals, and high metal coagulant
dosages, the phosphorus content of effluent suspended solids
is significantly reduced.
• (Reason: at very high metal dosages, a larger proportion of
the precipitates formed are metal hydroxides.)
 Effect of Temperature on
Coagulation
• Temperature significantly affects coagulation operations,
particularly for low turbidity waters, by shifting the optimum
pH. This can be mitigated by operating at an optimum pOH as
given by:
pH + pOH = pKW
Where pKW = 0.01706xT + 4470.99/T – 6.0875
and T = temperature in °K = 273.15 + °C.
• One advantage of the pre-polymerized coagulants such as
PACl and polyferric sulfate is that they potentially can be
tailored for particular raw water conditions such as
temperature and other parameters, and can be less sensitive
to changes in temperature.
 Sequence of Chemical Addition:
Effect on Coagulation
• Traditionally, the sequence of chemical addition for
coagulation operations is to first add chemicals for pH
correction, then add the metal coagulant, then add the
flocculant aid.
• sequence logic is important.
• Other sequences are more effective, including inverting the
sequence of metal coagulant and polymer addition, and the
sequence of metal coagulant addition and pH adjustment.
• The best sequence for a particular application can be
determined by jar test experiments.
 Residual aluminum
• Residual aluminum in treated water because
– is undesirable for aesthetic reasons,
– a possible link between aluminum and adverse neurological effects
such as Alzheimer’s disease.
• Although ingestion from drinking water constitutes a
relatively small proportion of daily intake, residual aluminum
in treated waters can be minimized by proper adjustment of
pH.
 Residual aluminum
• Relationship between residual aluminum and treatment pH
• The optimum pH to minimize residual aluminum also depends
on other substances in solution.
• For example, the presence of fluoride in the raw water shifts
the pH of minimum Al residual upwards towards 7, depending
on the fluoride concentration.

Compilation of residual
aluminum determined from jar
tests using membrane filters
ranging from 0.05 to 0.45 µm
 Residual aluminum
• The presence of NOM: complexation of aluminum species
with humic substances, the residual aluminum is linked to the
removal of NOM.
• For example, at low alum dosages applied to humic waters,
residual aluminum concentrations after treatment can be
relatively high.
• At higher applied alum dosages, where a larger proportion of
the humic substances are removed, residual Al concentrations
after treatment are often significantly lower.
• This reduction in residual aluminum with higher aluminum
dosages has also been found during fluoride removal.
 Residual aluminum
• colloidal material contributes to aluminum residual  it is
important to achieve low final treated water turbidities, at
least less than 0.1 NTU, to minimize final aluminum residuals.
• When addressing high aluminum residuals, it is also important
to determine whether the aluminum is in the particulate
form, which would indicate improvements to filter retention,
or whether it is soluble, which would require improving the
chemistry of coagulation – particularly the pH before
filtration.
 Rapid Mixing
• include in-line mixers either with or without controlled
velocity gradients
• In general, in-line mixers provide the best rapid mixing
conditions.
• In-line mixers without velocity gradient control include static
mixers, orifice plates, diffuser grids in an open channel,
and hydraulic jumps in open channels.
• In each of these cases, the velocity gradient and degree of
mixing is dependent on the flow rate.
 Rapid Mixing
• In-line mixers with velocity
gradient control include in-
line mechanical mixers with
variable speed impellers,
and in-line jet mixers.
• In-line jet mixers: the
velocity gradient is varied by
the flow rate though the jet
nozzle. Typically these are
mounted concentrically
within an enclosed pipe,
with the jet discharging
in-line jet mixer
against the flow.
 Design of Coagulant Chamber

https://image.slidesharecdn.com/pptcoagulationandflocculation-160331111058/95/ppt-coagulation-and-flocculation-19-1024.jpg?cb=1459422671
 Rotating Blade Flocculators

vertical paddle (courtesy horizontal (reel) paddle axial flow (courtesy top-
Amwell) (courtesy WesTech); right: Anco; bottom-right:
Philadelphia Mixers)
 Flocculator
• An advantage of horizontal shaft units is that
compartmentalization is simple. With adjacent sections along
the drive shaft carrying different configurations of agitators,
different tapered G values are produced for one particular
drive shaft rotational speed.
• With most designs of horizontal shaft flocculators, the
provision of stators within the flocculation basin to minimize
rotation of the water with the blades is difficult.
 Flocculator
• The principal advantages of vertical shaft rotary devices are
that underwater bearings are not required; the drive unit is
above the water level and the arrangement for stators is
simple.
• two basic types, axial flow, and turbine flocculators
• A disadvantage of turbine flocculators is that there is a much
wider diversity of G values within the flocculation basin for a
given mean velocity gradient - being high in the vicinity of the
device and low near the walls of the basin.
• Such devices generally provide
lower flocculation performance when compared with devices
accommodating as much of the flocculation basin volume as
possible.
 Efficiency of Coagulation-
Flocculation: Factors
1. Type of coagulant used
2. Coagulant dosage
3. Final pH
4. Coagulant feed concentration
5. Type and dosage of chemical
additives other than primary
coagulant (e.g. polymers)
6. Sequence of chemical addition
and time lag between dosing
points
7. Intensity and duration of mixing
at rapid mix stage
8. Type of rapid mix device
9. Velocity gradients applied
during flocculation stage
10. Flocculator retention time
11. Type of stirring device used
12. Flocculator geometry.
 Advantages
• Simplicity and cost-effectiveness
• Separates many kind of particles from water
• Enhances filtration process
• Uses abundant and low cost chemicals
 Disadvantages
• Input of chemicals required
• Qualified personnel required for design (e.g.
construction of chambers and dosage of
chemicals) and system maintenance
• Transfer of toxic compounds into solid phase
and formation of sludge that has to be treated
subsequently
• Relatively time consuming process
For EnE 203 Class use only. References of Photos and notes are still to be
indicated.
Main Reference on lecture photos and equations:
http://www.sswm.info/content/coagulation-flocculation

QUESTIONS?