Coagulation and Flocculation

Coagulation-flocculation
Employed for removal of colloidal and also suspended
materials
Colloids of wastewater are 0.01 to 1 micron in size and have
net negative surface charge
Colloids are stable and show brownian motion
Coagulation flocculation involves destabilizaion of colloids by
chemical dosing and floc formation by particle collisions
Typical coagulants and flocculants –
– Natural and synthetic organic polymers
– Metal salts such as alum or ferric sulfate
– Prehydrolized metal salts such as ployaluminum chloride
and polyiron chloride
Flocculants are also used to enhance performance of
granular medium filters and in the dewatering of digested
biosolids (filter aids)
 Colloids
Either hydrophobic or hydrophilic
• Hydrophobic colloids (like clay)
– possess no affinity for the liquid medium
– lack stability in the presence of electrolytes
– readily susceptible to coagulation
• Hydrophilic colloids (like proteins)
– have marked affinity for water
– absorbed water retards flocculation and may require special
treatment
• Association colloids
– Typically made up of surface active agents like soaps, synthetic
detergents and dyestuffs (form organized aggregates, micelles
• Stability of colloids
– Property that prevent agglomeration and settling of colloids
– Electrical properties are responsible (create repelling force)
– In case of hydrophilic colloids, the absorbed envelope of water also
contributes to stability
 Psi potential and Zeta Potential
• Fixed layer of electrical charge results in the accumulation
of a cloud of ions around a colloid particle
– Charge on the colloid depends on the chemical composition
of the medium and nature of the colloid
– Surface charge develops from
• isomorphous replacement – ions in the lattice structure are
replaced by ions from solution (occurs in clay and other soil
particles)
• structural imperfections – broken bonds on the crystal edge and
imperfections in the crystal formation are responsible (clay and
similar particles)
• preferential adsorptions – oil droplets, gas bubbles and
chemically inert substances dispersed in water acquire negative
charge from preferential adsorption of anions (OH-)
• Ionization – proteins or microorganisms – ionization of carboxyl
and amino groups
– Neutralization of the particle charge due to the fixed layer of
stabilizing ions of colloids can induce flocculation
 Psi potential and Zeta potential
• Within the cloud of ions a double layer of ions can be
distinguished around the colloid
– Layer of ions within the slipping plane
– As the particle moves this layer of ions also move along
– Thickness depends on the concentration and valence of
nonspecific electrolytes
• There is potential difference between the colloidal particle
surface and the body of the fluid – it drops in the interface
– Depends on the colloid charge & the double layer thickness
– Psi () potential - Potential drop between the surface of the
colloid and the body of solution
– Zeta () potential - Potential drop between the slipping
plane and the body of the solution
– zeta potential can be measured but not the Psi potential
 Zeta potential
A measure of the magnitude of charge and resulting
degree of stability – can be determined by
4 4EM
  
X 
Here
 Zeta potential (mV)
v particle velocity
 dielectric constant of the medium (80.36 for water)
 viscosity of the medium (0.01 poise for water)
X applied potential per unit length of cell (in V/cm)
EM electrophoretic mobility, (m/s)/(V/cm) – estimated by
v/X
At 25°C its value can be determined by
 = 12.8 EM
 Zeta potential
Determination involves measurement of colloidal particles’
mobility across a cell (as viewed through a microscope)
• Since there will be statistical variation in the mobility, mobility of
20 or 30 individual colloid particles is actually taken
• Lazer Zee meter wherein achieving a stationary cloud of
particles is used as the basis of measurement
Zeta potential for water and wastewater colloids is in the
range of –12 to –40 mV
• Unaffected by pH over a range of 5.5 to 9.5 pH
• Can be lowered by
• Change of concentration of potential determining ions
• Addition of ions of opposite charge
• Contraction of the diffuse part of the double layer by increasing the
ion concentration of the medium
For effective coagulation to occur zeta potential should be
around zero (iso-electric point), in the range of ±0.5 mV
• Majority of colloids have negative zeta potential and can be
lowered by addition of high valence cations
(Na+ : Mg2+ : Al3+ = 1 : 63 : 570)
 Coagulation
Particle-particle interactions are extremely important in
brining about aggregation by means of brownian
motion
• Two principal forces, forces of repulsion (due to electrical
charges) and van der Waals forces of attraction, are
involved
– Van der Waals forces of attraction come into play when two
particles come in close proximity to each other
• Net force (repulsion–attraction) curve indicates an energy
barrier to be overcome for holding the particles together
– For microflocculation there should not be any energy barrier
to overcome
– Reducing repulsive forces can reduce the net energy barrier
and microflocculation becomes possible
 Coagulation
• Microflocculation requires
– Addition of potential determining ions (lessen surface
charge)
• charge reversal of the double layer and development of
new stable particles can also be possible
– Addition of electrolytes
• reduce thickness of the diffuse electric layer (or double
layer)
• Critical Coagulation Concentration for colloids
destabilization to occur
• Increasing concentration of indifferent electrolyte will not
result in restabilization of destabilized colloids
 Mechanism of coagulation
Theory of chemical coagulation reactions is very complex
Coagulation reactions are often incomplete and numerous
side reactions with other substances of wastewater
Occurs by two mechanisms: perielectric (or electrokinetic)
coagulation and orthokinetic coagulation
• Perielectric coagulation: ions or colloids of opposite
charge reduce the zeta potential to a level below van der
Waals forces
– High valence cations depress particle charge and effective
thickness of the double layer and reduces the zeta potential
– In the acidic range microflocs retain positive charge because
of adsorption of H+, and can in turn neutralize other colloids
– In most wastewaters perielectric coagulation occurs
• Orthokinetic coagulation: micelles aggregate and form
clumps that agglomerate the colloidal particles
– Agglomerates colloids with a hydrous oxide floc – colloids
can also get removed by enmeshment in the floc
 Mechanism of coagulation
Flocculation is two types
• Microflocculation (perikinetic flocculation)
– Brought about by brownian motion
• Macroflocculation (orthrokinetic flocculation)
– Particle aggregation is brought about by inducing velocity gradient
and mixing and by differential settling
– ineffectual until the colloidal particles reach a size of 1 to 10
microns
Sequence of operations for effective coagulation
• If necessary add alkalinity (bicarbonate is best - will not rise pH)
• Add alum/ferric salts next – forms positively charged microflocs
• Rapid mixing for 1 to 3 minutes
• Add coagulant aids (activated silica and/or polyelectrolyte) last
for floc buildup
– Coagulant aids (polymers) are 10 to 15 times more effective than
coagulants but are more expensive
 Coagulants: Alum
Alum (aluminum sulfate, Al2(SO4)3-18H2O) is the most popular
coagulant in waste treatment
Al2 ( SO4 )3 .18H 2O  3Ca (OH ) 2  3CaSO 4  2 Al (OH )3  18H 2O
Chemical form of aluminum hydroxide is actually Al2O3.xH2O, and
this is amphoteric
Under acidic conditions the hydroxide dissociates and at pH 4.0,
51.3 mg/l of Al3+ is in solution
Al (OH )3  3H   Al 3   3H 2O
Under alkaline conditions the hydrous aluminum oxide dissociates to
form AlO2- and at 9.0 pH 10.8 mg/l of aluminum is in solution as
AlO2-

Al2O3  2OH   2 AlO2  H 2O
Alum floc is positively charged below 7.6 pH and negatively charged
above 8.2 pH, and it is least soluble at 7 pH
High alum doses in treating some industrial wastewaters can cause
postprecipitation of flocs depending on the pH of flocculation
 Coagulants: Ferric salts
Ferric salts (ferric chloride and ferrous sulfate)
– Produce insoluble hydrous ferric oxide [Fe(OH) 3]in the pH
range 3.0 to 13.0
– Below 6.0 pH floc is positive and above 8.0 pH it is negative
– Presence of anions alter the range of effective flocculation –
chlorides increase the range slightly on both the sides – sulfate
increases range in the acidic region
Lime
– Is not a true coagulant
– Reacts with bicarbonate alkalinity and precipitate as CaCO 3
– Reacts with ortho-phosphate to precipitate calcium
hydroxyapatite
– Lime sludge can be dried and calcinated for reuse
Magnesium hydroxide
– Precipitates at high pH levels
– Good clarification requires presence of some gelatinous
magnesium hydroxide
– Sludge becomes more difficult to dewater
Destabilization by hydrolysed metal ions
Aggregation brought about by the addition of alum or ferric sulfate
is a complex process
• Hydrolysis products of Al3+ and Fe3+ are apparently
responsible for the aggregation
• Metal ions must be forming amphoteric coordination compounds
– Central metal ion is surrounded by and attached to ligands by
coordinate covalent bonds through ligand donor atoms
– Carbonate, chloride, hydroxide, ammonia and water are important
ligand groups in wastewater
• Effectiveness of aluminum and iron varies with time
Action of hydrolysed metal ions is divisible into three categories:
• Adsorption and charge neutralization
– Coagulant added for charge neutralization is more, excess metal
forms hydroxide precipitates and soluble metal hydrolysis products
• Adsorption and inter-particle bridging
• Enmeshment in sweep floc
 Sequence of reactions and events
occurring during coagulation-flocculation
Divided into four zones
• Zone-1: Coagulant added is not sufficient to destabilize colloids
• Zone-2: Colloidal particles are destabilized - If allowed these
flocculate and settle and residual turbidity is reduced
• Zone-3: With addition of more coagulant surface charge of colloids
is reversed and the particles are restabilized
• Zone-4: With more addition of coagulant large amount of hydroxide
flocs are formed - as these flocs settle, the colloids are removed by
sweep action
Doses at which different zones are reached depends on
• pH and temperature of the wastewater
• Nature of the colloidal particles
 Solubility of Metal Ions during
Coagulation-flocculation
Solid lines in the figure trace approximate total concentration
of residual soluble alum and iron after precipitation
• Optimum region for alum precipitation is 5-7 pH and
minimum solubility is at 6 pH
– Optimum particle removal by sweep floc in pH range 7-8
with alum dose of 20-60 mg/l for many wastewaters
• Optimum region for iron precipitation is 7-9 pH and
minimum solubility is at 8 pH
 Coagulant aids
Promote growth of large and rapidly settling flocs
Activated silica (a short chain polymer) – binds together
particles of micrfine aluminum hydrate – usual dosage is 5-10
mg/l - high dosages inhibit floc formation because of its
electronegative properties
Polyelectrolytes: high molecular weight polymers containing
adsorbable groups – form bridges between particles or charged
flocs – dosages are 1 to 5 mg/l – substatially unaffected by pH –
can serve as a coagulant itself
Two categories: natural (polymers of biological origin such as
alginates and cellulose derivatives) and synthetic
Coagulant added begin polymerization in a fraction of second after
being added to water
– Initial and rapid mixing is hence of critical importance specially
when the metal ions are to be used as coagulants
 Coagulant aids
Synthetic polyelectrolytes consist of simple monomers
plymerized into high molecular weight substances
Three types of synthetic polyelectrolytes:
– Cationic (adsorbs on negative colloid or floc particles) – dose
is 2-5 mg/l – preferred where the buildup of inert chemical is
to be avoided
– Anionic (replace anionic groups on a colloidal particle and
permit hydrogen bonding between the colloids and the
polymer) – dose is 0.25 to 1.0 mg/l – tough flocs can be
formed and speeds up flocculation and settling
– Nonionic (adsorbs and flocculates by hydrogen bonding
between the solid surfaces and the polar groups in the
polymers) – dose is 0.25 to 1.0 mg/l – tough flocs can be
formed and speeds up flocculation and settling
 Coagulant aids

Cationic poly-electrolytes can act as coagulant and cause charge

neutralization of negatively charged colloids of wastewaters - for
better charge neutralization mixing intensity must be high
otherwise the polymer molecule can fold back on itself – colloid
concentration should be high otherwise dose of polyelectrolyte
should be high
Polyelectrolytes form interparticle bridge – two or more particles
become absorbed along the length of the polymer – initial
mixing of the polymer and the wastewater with colloids must be
accomplished in a matter seconds
Extremely high molecular weight cationic polyelectrolytes bring
about coagulation by charge neutralization and bridging
phenomenon
 Finding Optimum pH and Optimum
Doses of Coagulant & Polyelectrolyte
for Coagulation-flocculation
Laboratory experimentation is essential
Two procedures, Jar test and Zeta potential control (towards
zero), can be followed
Find rough dose of coagulant at 6 pH
• Take known volume of sample and adjust its pH to 6
• Add coagulant in small increments till visible flocs appear
• After each addition rapid mix for 1 min. and slow mix for 3 min.
and observe for visible flocs
Find optimum pH
• Take one liter of sample into each of the six beakers of Jar Test
Apparatus and adjust pH to 4, 5, 6, 7, 8 and 9
• Apply rough dose to all the samples, rapid mix the samples for 3
min., then slow mix for 12 min. and then allow to settle the
formed flocs for 30 min.
• Measure turbidity of supernatant in each of the samples and find
optimum pH for coagulation-flocculation
 Finding Optimum pH and Optimum
Doses of Coagulant and Polyelectrolyte
Find optimum dose of the coagulant
• Take a liter sample into the 6 beakers and adjust to optimum pH
• Apply a range of coagulant doses (50% to 150% of the rough
dose) to the samples, rapid mix for 3 min., then slow mix for 12
min. and then allow flocs to settle for 30 min.
• Measure turbidity of supernatant in each of the samples and find
optimum dose of coagulant for coagulation-flocculation
Find optimum dose of the polyelectrolyte
• Take a liter sample into the 6 beakers and adjust to optimum pH
• Apply optimum dose of coagulant to all, rapid mix for 3 min. and
then apply a range of doses of the polyelectrolyte (upto 5 mg/l)
• Slow mix the samples for 12 min. and then allow the flocs to
settle for 30 min.
• Measure turbidity of supernatant in each of the samples and find
optimum dose of the polyelectrolyte
 Coagulation Equipment
Conventional system: includes a rapid mixing tank, a
flocculation tank containing longitudinal paddles and
conventional settling tank
System that includes a rapid mixing tank and a
clari-flocculator: combines both flocculation and
settling
Sludge blanket unit: combines mixing, flocculation and
settling in a single unit
• Settled sludge recirculation is often practiced
– Reduces both coagulant dose and the time for floc formation
– Increases efficiency (possible blanket settling is considered
responsible)
 Waste treatment by coagulation
flocculation
Waste containing emulsified oils can be clarified by
coagulation
• Emulsion can be broken by
– Salting out with salts like calcium chloride
– Lowering of the pH
• Alum and polyelectrolyte can be used for the coagulation
flocculation
Presence of anionic surface agents in the waste increase the
coagulant dose required
Wastes containing synthetic anionic detergent may need
cationic surfactant to neutralize the detergent
There are instances where pH of coagulation-flocculation is
• as high as 11 - textile waste
• as low as 3 - waste from latex base paints manufacturing