Chapter 5

CHEMICAL
TREATMENT
 Definition
Treatment of wastewater in which change is
brought about by means or through chemical
reaction
Chemical process in wastewater treatment :
Chemical precipitation / Coagulation
Disinfection
Dechlorination Tertiary / Advance Treatment

Adsorption
Chemical Precipitation

The addition of chemicals to alter the

physical state of the dissolved and
suspended solid and to facilitate their
removal by sedimentation
In some processes, the removal involves
coagulation process
Coagulation - Flocculation
Although the words "coagulation" and
"flocculation" are often used
interchangeably they refer to two distinct
processes
Coagulation indicates the process
through which colloidal particles and very
fine solid suspensions are destabilized so
that they can begin to agglomerate if the
conditions are appropriate
 Flocculation refers to the process by
which destabilized particles actually
conglomerate into larger aggregates so
that they can be separated by gravity
Colloidal particles
Typical colloidal characteristics for water
and wastewater:
Size range: 0.001 to 1 micron (some where in
the range between a molecule and bacteria in
size)
Most of nonsettleable solids are colloidal
particulates
Colloid in wastewater mostly have (-) charge
therefore coagulation can be done through
addition of high valence cation
The following graphic shows some size characteristics
for particulates in water and wastewater
COAGULANT in WASTEWATER
TREATMENT
Mainly aluminum and iron salts
Aluminum sulfate
Ferrous sulfate
Ferric sulfate
Ferric chloride
Lime [Ca(OH)2]

Aluminum salts are cheaper but iron

salts are more effective over wider pH
range
Aluminum Sulfate
Properties :
Acidic ( corrosive )
Floc charges :
(+) at pH 7.6
Processing pH range : 5.5 -7.6
(-) at pH 8.2

To produce the hydroxide floc, enough

alkalinity should present in the water
Reaction :
Ferrous Sulfate
Properties :
Produces floc > alum
Processing pH range : 4 9

Reaction :

+ 2 H2O
Ferric Sulfate

Properties :
Corrosive
It reacts with alkalinity presents in water

Fe(OH)3 is dense and settle fast

Optimum pH is between 4 and 12

Reaction :
 If the alkalinity is insufficient lime can be
added:

+ 6 CO2
Ferric Chloride

Properties
Corrosive
It reacts with natural alkalinity

Optimum pH is 4 12

Reaction

6 CO2
 If the alkalinity is insufficient lime can be
added:
Lime
Slaked lime or hydrated lime are used
Slaked lime [Ca(OH)2] : produced by
reacting quicklime [CaO] with water
If the wastewater is acidic the lime
addition will go first toward the
neutralization of the acid before colloid
removal can take place
 Reaction :

or
Ca(OH)2 + H2CO3 CaCO3 + 2 H2O
CAOGULANT DOSAGE
Determination of coagulant dosage are carried
out using jar test
A jar test simulates the coagulation and
flocculation processes
Jar test procedure :
Add different doses of the select coagulant to each jar
Rapid mix each jar at 100 to 150 rpm for 1 minute.
The rapid mix helps to disperse the coagulant
throughout each container
Reduce the stirring speed to 25 to 30 rpm and
continue mixing for 15 to 20 mins
This slower mixing speed helps promote floc
formation by enhancing particle collisions which lead
to larger flocs
Turn off the mixers and allow flocs to settle for 30 to
45 mins
Then measure the final residual turbidity in each jar
Plot residual turbidity against coagulant dose
 Optimum coagulant dose: 12.5 mg/L

Coagulant Dose mg/L

The coagulant dose with the lowest residual

turbidity will be the optimum coagulant dose
COAGULATION PROCESSING
Rapid Mixing (Coagulation)
Objective
To uniformly mix the coagulant with colloidal matters present
in raw water so as to bring about colloidal destabilization
How to achieve rapid mixing? L
Horizontal baffled tank
The water flows in horizontal W
direction. The baffle walls help
to create turbulence when the water Plan view (horizontal flow)
hit the surface and thus facilitate mixing
Vertical baffled tank
The water flows in vertical H
direction. The baffle walls help to
create turbulence when the water hit
the surface and thus facilitate L
mixing Isometric View (vertical flow)
Mechanical Mixing
Slow & Gentle mixing (Flocculation)

Flocculator is designed mainly to provide

enough interparticle contacts to achieve
particles agglomeration so that they can be
effectively removed by sedimentation
During flocculation the average velocity
gradient is typically much lower than in rapid
mix devices
Horizontal Paddle Flocculator
Vertical Paddle Flocculator
COAGULANT AIDS

In some waters or effluents, coagulation is

poor, even with the best dose of coagulant
The addition of extra substances known as
coagulant aids can often result in considerable
improvement in coagulation and an increase in
the settling velocity of the resulting floc
Example of coagulants aids :
Activated silica
Polyelectrolyte
Activated Silica
Activated silica is a short chain polymer
capable of binding together aluminum hydrate
particles used in coagulation processes
Common dosage for activated silica is 5 10
ppm
At higher dosage will retard the process due to
( - ) charge
Polyelectrolyte
Contain absorbing functionality
Interparticles bridging
Heavy Metal Removal
Heavy metals include lead, silver, mercury,
copper, nickel, chromium, zinc, cadmium and
tin that must be removed to certain levels to
meet discharge requirements.
Chemical precipitation is one of the more
popular and economical methods for removing
heavy metals from industrial waste waters
Common precipitants include hidroxide (OH-),
carbonate (CO32-) or sulfide (S2-)
Pretreatment is frequently necessary to
remove Cyanide (CN ) and ammonia (NH3)
which tend to form complex with metal
Cyanide removal
CN can be removed by oxidation
process using :
Ozon, pH 6 10
KMnO4 , pH 12 14

Alkaline chlorination , pH > 10

 Alkaline chlorination
Ammonia removal
Reaction of ammonia in water :

Addition of lime to pH 10,5 11,5 will

move the reaction to the left
Ammonia gas will be removed in paked
tower using air as stripping gas
Hydroxide Precipitation

Precipitation by hydroxide formation is

the most common heavy metal
precipitation method
Many heavy metals are amphoteric.
Therefore their solubility reaches a
minimum at a specific pH (different for
each metal)
 The addition of caustic materials is used to raise the
pH. The most common caustics are :
sodium hydroxide (NaOH)

calcium hydroxide (Ca(OH)2; lime

Precipitation is frequently followed with addition of

coagulant and sedimentation for separation process
Sulfide Precipitation
Metal sulfides are typically very insoluble.
Therefore metals can be precipitated by
adding sulfide ions (S-2)
Metal sulfides have much lower solubilities
than the corresponding metal hydroxides, thus
allowing lower residual metal concentrations in
the treated wastewater
Sulfide precipitation is always conducted
under alkaline conditions to promote sulfide
ion formation.
Disadvantage of Sulfide Precipitation
Sulfide sludges are more prone to oxidation
resulting in resolubilization of the metals as
sulfates
Evolution of H2S is a potential hazard if the
pH is not carefully maintained in the alkaline
region
Carbonate Precipitation
Some metals (lead, cadmium, nickel) form
insoluble carbonates that can be used in
carbonate precipitation
Carbonate precipitation takes place only if
carbonate ions (CO3 -2) are present. Free
carbonate ions are present only if the pH is
high. A caustic is often added to raise the pH
High pHs also promote the precipitation of the
metals as hydroxides. Hence, carbonate
precipitation is often a co-precipitation