CH 6007 Wastewater Treatment

Dr. D. Balaji

Associate Professor
Department of Chemical Engineering

balajid@ssn.edu.in
OBJECTIVE:
To focus on the wastewater transport system and the
theory and design technique for the wastewater treatment
process.

OUTCOME:
Upon completion of this course, the students would have
knowledge on physical/chemical/biological characteristics
of and the evaluation technique for sewage.
CH6007 WASTEWATER TREATMENT LTPC
3 003

UNIT I WASTE WATER TREATMENT AN OVERVIEW 9

Terminology Regulations Health and Environment Concerns in waste water
management Constituents in waste water inorganic Organic and metallic constituents.
UNIT II PROCESS ANALYSIS AND SELECTION 9
Components of waste water flows Analysis of Data Reactors used in waste water
treatment Mass Balance Analysis Modeling of ideal and non ideal flow in Reactors
Process Selection.
UNIT III CHEMICAL UNIT PROCESSES 9
Role of unit processes in waste water treatment chemical coagulation Chemical
precipitation for improved plant performance chemical oxidation Neutralization
Chemical Storage.
UNIT IV BIOLOGICAL TREATMENT 9
Overview of biological Treatment Microbial metabolism Bacterial growth and
energatus Aerobic biological oxidation Anaerobic fermentation and oxidation
Trickling filters Rotating biological contractors Combined aerobic processes
Activated sludge film packing.
UNIT V ADVANCED WASTE WATER TREATMENT 9
Technologies used in advanced treatment Classification of technologies Removal of
Colloids and suspended particles Depth Filtration Surface Filtration Membrane
Filtration Absorption Ion Exchange Advanced oxidation process.
TOTAL : 45 PERIODS
 TEXT BOOKS

1. Waste water Engineering Treatment and Reuse: Mc Graw

Hill, G. Tchobanoglous, FI Biston, 2002.

2. Industrial Waste Water Management Treatment and

Disposal by Water Environment Federation Mc Graw Hill
III Edition 2008.
 Course Outcomes
On successful completion of this course, the student will be able
to
CO1: Understand the types of constituents present in the wastewater
and also its health effects.
CO2: Understand the design of types of reactors for treating different
kinds of wastewater and also to choose the right type of reactors for
the wastewater treatment.
CO3: Understand the different kinds of chemical unit processes in
the wastewater treatment.
CO4: Understand the different kinds of biological processes in the
wastewater treatment.
CO5: Understand the different types of advanced wastewater
treatment technologies.
CO6: Discuss water and wastewater treatment solid wastes
management and propose a treatment system for a given
wastewater to achieve a specified end use.
 Unit III Chemical Unit Processes

Role of unit processes in waste water treatment

Chemical coagulation
Chemical precipitation for improved plant performance
Chemical oxidation
Neutralization
Chemical Storage.
 Role of unit processes in waste water treatment
In the field of waste water treatment, chemical unit processes
are usually used in conjunction with the physical unit
operations and the biological unit processes, to meet treatment
objectives.
The principal chemical unit processes used for wastewater
treatment include chemical coagulation, chemical
precipitation, chemical disinfection, chemical oxidation,
advanced oxidation process, ion exchange and chemical
neutralization, scale control and stabilization.
Chemical precipitation helps in removal of phosphorus and
suspended solids in primary sedimentation facilities used for
physical-chemical treatment. Also heavy metals removal.
 Chemical adsorption are used for the removal of
organics not removed by conventional chemical and
biological methods.
They are also used for dechlorination of wastewater
before final discharge for treated effluent.
Disinfection is used for selective destruction of disease-
causing organisms which can be accomplished in various
ways.
It is important to remember that one of the inherent
disadvantages associated with most chemical unit
processes is that they are additive processes.
In most cases, something is added to the waste water to
achieve the removal of something else.
 The increase in the dissolved solids in the treated waste water
can be a significant matter if they are to be reused.
Chemical oxidation helps in removal of BOD, grease,
ammonia, etc., and in the destruction of microorganisms. They
are also used for the control of odors in sewers, pump stations
and treatment plants.
Advanced oxidation process removal of refractory organic
compounds.
Chemical stabilization helps in stabilization of treated
effluents.
Chemical scale control is used in the control of scaling due to
calcium carbonate and related compounds.
 Chemical coagulation the chemical destabilization of
particles in wastewater to bring about their aggregation during
perikinetic and orthokinetic flocculation.
Perikinetic flocculation (Microflocculation) refers to
flocculation (contact or collisions of colloidal particles) due to
Brownian motion of colloidal particles. The random motion of
colloidal particles results from their rapid and random
bombardment by the molecules of the fluid.
Orthokinetic flocculation (Macroflocculation) refers to
contacts or collisions of colloidal particles resulting from bulk
fluid motion, such as stirring.
Chemical neutralization control of pH
Ion Exchange Removal of ammonia , heavy metals, TDS
and removal of organic compounds.
Chemical Coagulation
Chemical Coagulation
Chemical Coagulation
 Chemical coagulation
Coagulation is the process of destabilizing colloidal particles so
that particle growth can occur as a result of particle collisions.
Chemical reactions are often incomplete, and numerous side
reactions with other substances in the wastewater.
The term flocculation is used to describe the process whereby
the size of particles increases as a result of particle collisions.
The term chemical coagulation includes all of the reaction
mechanisms involved in the chemical destabilization of
particles and in the formation of larger particles through
perikinetic flocculation (aggregation of particles in the size
range from 0.01 to 1m).
Coagulant is the chemical that is added to destabilize the
colloidal particles in wastewater so that floc formation can
result.
Chemical coagulation
The reactions and mechanisms involved in the chemical
destabilization of particles and in the formation of larger particles
through perikinetic flocculation (aggregation of particles in the size
range of 0.01 to 1 m).
Coagulant
It is the chemical that is added to destabilize the colloidal particles
in wastewater so that floc formation can result.
Flocculent
It is the chemical, typically organic, added to enhance the
flocculation process. The process whereby the size of particles
increases as a result of particle collisions.
Examples for coagulants and flocculants:
Natural and synthetic organic polymers, metal salts such as alum or
ferric sulfate, and prehydrolyzed metal salts such as polyaluminum
chloride (PACl) and polyiron chloride (PICI).
Types of flocculation
Microflocculation (perikinetic flocculation): particle
aggregation is brought about by the random thermal motion of
fluid molecules known as Brownian motion.
Macroflocculation (orthokinetic flocculation): particle
aggregation is brought about by including velocity gradients
and mixing in the fluid containing the particles to be
flocculated.
The purpose of flocculation is to produce particles, by means
of aggregation, that can be removed by inexpensive particle-
separation procedures such as gravity sedimentation and
filtration.
Nature of particles in wastewater
Suspended particles are generally larger than 0.1 m can be
removed by sedimentation.
Colloidal particles cannot be removed by sedimentation.
Invention is: Chemical coagulants and flocculent aids.
Removal of colloidal particles mainly depends on the
following characteristics of colloidal particles in wastewater.
1. Particle size and number
2. Particle shape and flexibility
3. Surface properties including electrical characteristics
4. Particle-particle interactions
5. Particle-solvent interactions
 1. Particle size and number
The size range of colloidal particles have been classified as
varying from 0.001 to 1 m.
The number of colloidal particles in untreated wastewater and
after primary sedimentation is typically in the range from 106
to 1012 / mL.
It is important to note that the number of colloidal particles
will vary depending on the location where the sample is taken
within the treatment plant.
The removal efficiency is depends on the number of particles
present in the wastewater.
 2. Particle shape and flexibility
Particle shapes found in wastewater can be described as
spherical, semispherical, ellipsoids of various shapes (e.g.,
prolate and oblate), rods of various length and diameter (e.g.,
E.coli), disk and disklike, strings of various lengths and
random coils.
Large organic molecules are often found in the form of coils
which may be compressed, uncoiled, or almost linear.
The shape of some larger floc particles is often described as
fractal.
The shape of the particle will affect the electrical properties,
the particle-particle interactions, and particle-solvent
interactions.
3. Surface properties including electrical characteristics

Development of the Surface Charge

1. Isomorphous replacement
2. Structural imperfections
3. Preferential Adsorption
4. Ionization

Measurement of the Surface Charge

1. Electrical double layer
2. Zeta potential
 Regardless of how it develops, the surface charge, which promotes
stability, must be overcome if these particles are to be aggregated
(flocculated) into larger particles with enough mass to settle easily.
Isomorphous replacement
Charge development through isomorphous replacement occurs in
clay and other soil particles, in which ions in the lattice structure are
replaced with ions from solution (e.g., the replacement of Si4+ with
Al3+ ).
Structural imperfections
In clay and similar particles, charge development can occur because
of broken bonds on the crystal edge and imperfections in the
formation of the crystal.
Preferential adsorption
When oil droplets, gas bubbles, or other chemically inert substances
are dispersed in water, they will acquire a negative charge through
the preferential adsorption of anions(particularly hydroxyl ions).
Ionization
In the case of substances such as proteins or
microorganisms, surface charge is acquired
through the ionization of carbonyl and amino
groups.
This ionization can be represented as follows,
where R represents the bulk of the solid
COO
R R COOH R COO
NH 2 NH 3 NH
2
At high pH at low pH at isoelectri c po int
4. Particle-particle interactions
 Particle-particle interactions are extremely important in
bringing about aggregation by means of Brownian motion.
In the interaction between two charged plates, there are two
principal forces involved that are the forces of repulsion, due
to the electrical properties of the charged plates, and the van
der Waals forces of attraction.
The net total energy shown by the solid lines is the difference
between forces of repulsion and attraction.
Although floc particles can form at long distances as shown by
the net energy curve, the net force holding these particles
together is weak and the floc particles that are formed can be
ruptured easily.
 Particle destabilization with potential-
determining ions and electrolytes
To bring about particle aggregation through
microflocculation, steps must be taken to reduce particle
charge or to overcome the effect of this charge.
The effect of the charge can be overcome by
Addition of potential-determining ions, which will be
taken up by or will react with the colloid surface to lessen
the surface charge
Addition of electrolytes, which have the effect of
reducing the thickness of the diffuse electric layer and,
thereby reduce the zeta potential.
Effect of addition of counterions and
electrolytes to colloidal solutions
 5. Particle-solvent interactions
There are three general types of colloidal particles in liquids:
hydrophobic (water-hating), hydrophilic (water-loving) and
association colloids.
The first two types are based on the attraction of the particle
surface for water.
Some water molecules will generally adsorb on the typical
hydrophobic surface, but the reaction between water and
hydrophilic colloids occurs to a much greater extent.
The third type of colloid is known as an association colloidal,
typically made up of surface-active agents such as soaps,
synthetic detergents, and dyestuffs which form organized
aggregates known as micelles.
Chemical precipitation
 Chemical precipitation

It involves the addition of chemicals to alter the

physical state of dissolved and suspended solids and
facilitate their removal by sedimentation.
TSS and BOD removal.
The precipitation reactions that occur when various
chemicals are added to improve the performance of
waste water treatment facilities
The chemical reactions involved in the precipitation
of phosphorous from wastewater
 Some of the more important theoretical aspects of chemical
precipitation.
These computations are used to determine the quantities of
sludge produced as a result of the addition of various
chemicals.
Importance of chemical precipitation
As a means of improving the performance of primary
settling facilities
As a basic step in the independent physical-chemical
treatment of wastewater
For the removal of phosphorus and heavy metals.
 Chemical precipitation for improving
plant performance
In the past, they were used to enhance the degree of suspended
solids and BOD removal
Where there are seasonal variations in the concentration of
the waste water
Where an intermediate degree of treatment is required and
As an aid to the sedimentation process.
It removes about
80 to 90 % of the total suspended matter
40 to 70 % of the BODs
30 to 60 % of the CODs
80 to 90 % of the bacteria
While plain sedimentation removes
50 to 70 % of the total suspended matter
30 to 40 % of the organic matter settles out

Chemicals used in waste water treatment are

Alum,
Aluminium chloride,
Ferric chloride,
Ferric sulfate,
Ferrous sulfate,
Calcium hydroxide (Lime).
Sodium aluminate
 Alum
When alum is added to wastewater containing calcium and
magnesium bicarbonate alkalinity, a precipitate of aluminium
hydroxide will form.
The insoluble aluminium hydroxide is a gelatinous floc that
settles slowly through the wastewater, sweeping out suspended
material and producing other changes.
The reaction is exactly analogous when magnesium
bicarbonate is substituted for the calcium salt.
If less than the required amount of alkalinity is available, then
lime is added. Bit it is seldom required in the chemical
treatment of wastewater.
 Alum
When alum is added to wastewater containing calcium and
magnesium bicarbonates alkalinity, the reaction that occurs
may be illustrated as follows:

3Ca( HCO3 ) 2 Al 2 (SO 4 )3 .18H 2O 2Al(OH )3 3CaSO 4

6CO 2 18H 2O
The other chemicals like ferrous sulfate, lime, ferric chloride
can also be added for the wastewater treatment
 Lime
When lime alone is added as a precipitant, the principles of
clarification are explained by the following reactions:
H 2CO 3 Ca(OH ) 2 CaCO 3 2H 2O
3Ca( HCO 3 ) 2 Ca(OH ) 2 2CaCO 3 2H 2O

A sufficient quantity of lime is added to combine with all the

free carbonic acid and with the carbonic acid of the
bicarbonates to produce calcium carbonate.
Much more lime is generally required when it is used alone
than when sulfate of iron is also used.
Where industrial wastes introduce mineral acids or acid salts
into the wastewater, these must be neutralized before
precipitation can take place.
Ferrous sulfate and Lime
In most cases, ferrous sulfate cannot be used alone as a
precipitant because lime must be added at the same time to
form a precipitate.
When ferrous sulfate alone is added to a wastewater, the
following reaction occur:
FeSO 4 .7 H 2O Ca( HCO 3 ) 2 Fe( HCO 3 ) 2 CaSO 4 7 H 2O
Fe( HCO 3 ) 2 Fe(OH ) 2 CO 2
If sufficient alkalinity is not available, lime is often added in
excess in conjunction with ferrous sulfate:
Fe( HCO3 ) 2 2Ca(OH ) 2 Fe(OH ) 2 2CaCO3 2H 2O

The ferrous hydroxide can be oxidized to ferric hydroxide:

Fe(OH ) 2 1 / 2O 2 1 / 2H 2O Fe(OH )3
Ferric Chloride
Because of many problems associated with the use of ferrous
sulfate, ferric chloride is the iron salt used most commonly in
precipitation applications.
FeCl 3 3Ca( HCO3 ) 2 Fe(OH )3 3CaCl 2 6CO 2

Ferric Chloride and Lime

If lime is added to supplement the natural alkalinity of the
wastewater, the following reaction can be assumed to occur:
FeCl 3 3Ca(OH ) 2 2Fe(OH )3 3CaCl 2
Ferric Sulfate and Lime
The overall reaction that occurs when ferric sulfate and lime
are added to wastewater:
Fe 2 (SO 4 )3 3Ca(OH ) 2 2Fe(OH )3 3CaSO 4
Independent Physical-Chemical Treatment
Chemical precipitation for phosphorus removal

1. The chemistry of phosphate precipitation,

2. Strategies for phosphorus removal,
3. Phosphorus removal using metal salts and polymers
and
4. Phosphorus removal using lime
Chemistry of Phosphate precipitation
Addition of multivalent metal ions that form precipitates of
sparingly soluble phosphates.
Multivalent metal ions such as calcium [ca(II)], aluminum
[Al(III)], and iron [Fe(III)].
Polymers have been used effectively in conjunction with alum
and lime as flocculent aids.

Phosphate precipitation with calcium

10Ca 2 6PO 34 2OH Ca10 ( PO 4 ) 6 (OH ) 2

( Hydroxylapatite)
Phosphate precipitation with Aluminum and Iron

Al 3 H n PO 34n AlPO 4 nH

Phosphate precipitation with Iron

Fe 3 H n PO 34n FePO 4 nH
Strategies for Phosphorus removal
1. Pre-precipitation,
The addition of chemicals to raw wastewater for the
precipitation of phosphorus in primary sedimentation
facilities.
The precipitated phosphate is removed with primary sludge.
2. Co-precipitation
The addition of chemicals to form precipitates that are
removed along with waste biological sludge.
Chemicals can be added to (1) the effluent from primary
sedimentation facilities, (2) the mixed liquor (in the ASP), (3)
the effluent from a biological treatment process before
secondary sedimentation
Post-precipitation
Post-precipitation involves the addition of chemicals to the
effluent from secondary sedimentation facilities and the
subsequent removal of chemical precipitates.
In this process, the chemical precipitates are usually removed
in separate sedimentation facilities or in effluent filters.
 Factors affecting the choice of chemical for
phosphorus removal

1. Influent phosphorus removal

2. Wastewater suspended solids
3. Alkalinity
4. Chemical cost (including transportation)
5. Reliability of chemical supply
6. Sludge handling facilities
7. Ultimate disposal methods
8. Compatibility with other treatment processes
Chemical precipitation for removal of heavy metals
and dissolved inorganic substances

Common precipitants: hydroxide (OH) and sulfide (S2-) .

Carbonate (CO32-) has also been used in some special cases.
Metals may be removed separately or co-precipitaed with
phosphorus.
Metals: Arsenic, barium, cadmium, copper, mercury, nickel,
selenium, and zinc.
 Chemical oxidation
Chemical oxidation in wastewater treatment typically involves
the use of oxidizing agents such as ozone (O3), hydrogen
peroxide (H2O2), permanganate (MnO4), chloride dioxide
(ClO2), chlorine (Cl2 ) or (HOCl), and oxygen (O2), to bring
about change in the chemical composition of a compound or a
group of compounds.
Fundamentals of chemical oxidation
Oxidation-reduction reactions
Half reaction potentials
Reaction potentials
Equilibrium constants for redox equations
Rate of oxidation-reduction reactions
 Oxidation-Reduction Reactions
Oxidation-Reduction reactions (Redox equations) take place
between an oxidizing and a reducing agent.
In oxidation-reduction reactions both electrons are exchanged
as are the oxidation states of the constituents involved in the
reaction.
While an oxidizing agent causes the oxidation to occur, it is
reduced in the process. Similarly, a reducing agent that causes
a reduction to occur is oxidized in the process.
Example Cu2+ + Zn Cu + Zn2+
Cu changes from a +2 to zero oxidation state and the Zn
changes from a zero to a +2 state.
Because of the electron loss or gain, oxidation-reduction
reactions can be separated into two half reactions.
 The oxidation half reaction involves the loss of electrons while
the reduction half reaction involves the gain of electrons.
The two half reactions that comprise are as follows:
Zn 2e- Zn2+ (oxidation)
Cu2+ + 2e- Cu (reduction)
Referring to the above equations, there is a two-electron
change.
 Half-Reaction Potentials
Of the many properties that can be used to characterize
oxidation-reduction reactions, the electrical potential (i.e.,
voltage) or emf of the half reaction is used most commonly.
Thus, every half reaction involving an oxidation or reduction
has a standard potential Eo associated with it.
2+
Cu + 2e Cu Eo = 0.34 volt
-

Zn + 2e Zn Eo = - 0.763 volt
- 2+

The half-reaction is a measure of the tendency of a reaction to

proceed to the right. Half reaction with large positive
potential, E, tend to proceed to the right as written.
Conversely, half reactions with large negative potential, E,
tend to proceed to the left.
 Reaction potentials
The tendency of the reaction to proceed is obtained by
determining the Ereaction for the entire reaction as given by the
following expression
Ereaction = Ereduction Eoxidation
Where Ereaction = potential of the overall reaction
Ereduction = potential of the reduction half reaction
Eoxidation = potential of the oxidation half reaction
Equilibrium Constants for Redox Equations
The equilibrium constant for oxidation reduction reactions is
calculated using the Nernst equation as defined below.
nFE oreaction
ln K
RT
nFE oreaction
log K
2.303RT
Where
K equilibrium cons tan t
n number of electrons exchanged in the overall reaction
F Faraday' s cons tan t 96,485 C / g eq
Eoreaction Re action potential
R Universal gas cons tan t (8.314 J / mol K )
T Temperature (K )
 Rate of Oxidation-Reduction Reactions

The reaction potential provides no information about the rate

at which the reaction will proceed.
Chemical oxidation reaction often require the presence of one
or more catalysts for the reaction to proceed or to increase the
rate of reaction.
Transition metal cations, enzymes, pH adjustment, and a
variety of proprietary substances have been used as catalysts.
 Application of chemical oxidation

Chemical oxidation is now commonly used to

prove the treatability of nonbiodegradable (refractory)
organic compounds,
Eliminate the inhibitory effects of certain organic and
inorganic compounds to microbial growth and
Reduce or eliminate the toxicity of certain organic and
inorganic compounds to microbial growth and aquatic
flora.
Chemical Neutralization, Scaling control and
Stabilization
The removal of excess acidity or alkalinity by treatment with a
chemical of the opposite composition is termed as
neutralization.
Generally, all treated wastewaters with excessively low or high
pH will require neutralization before they can be dispersed to
the environment.
Scaling control is required for nanofiltration and reverse
osmosis treatment to control the formation of scale, which can
severely impact performance.
Chemical Stabilization is often required for highly treated
wastewater to control their aggressiveness with respect to
corrosion.
 pH Adjustment
A number of chemicals are available that can be used, the
choice will depend on the suitability of a given chemical for a
particular application and prevailing economics.
Sodium hydroxide and sodium carbonate, although somewhat
expensive, are convenient and are used widely by small plants
or for treatment where small quantities are adequate
Lime, which is cheaper but somewhat less convenient, is the
most widely used chemical.
Lime can be purchased as quicklime or slaked hydrated lime,
high-calcium or dolomite lime, and in several physical forms.
Limestone and dolomite limestone are cheaper but less
convenient to use and slower in reaction rate.
 Calcium and magnesium chemicals often form sludge that
require disposal.
Alkaline wastes are less of a problem than acid wastes but
nevertheless often require treatment.
In some treatment plants, carbon dioxide in the form of flue
gas has been used to neutralize alkaline wastewaters, as
illustrated by the following reactions:
2OH + CO CO +H O
- 2-
2 3 2
CO3 + CO + H O 2HCO
2- -
2 2 3
Based on the chlorine dose used for disinfection, the pH of the
disinfected effluent will be lower than that allowed for reuse
applications and for dispersal to the environment.
 In such cases, neutralization is controlled by automatic
instruments using a feedback loop, and the final effluent pH is
recorded.
Depending on the sensitivity of the environment, two-stage
neutralization may be required.
The reagent chemicals can be fed automatically, in the form of
solutions, slurries, or dry materials.
It the reaction rate is slow, instrumentation and control design
must take this factor into account.
 Scaling control
Usually, CaCO scale control can be achieved using one or more
3
of the following methods:
Acidifying to reduce pH and alkalinity
Reducing calcium concentration by ion exchange or lime
softening.
Adding a scale inhibitor chemical (antiscalant) to increase the
apparent solubility of CaCO in the concentrate stream
3
Lowering the product recovery rate.
Because it is not possible to predict a priori the value of pH in
water treated with reverse osmosis, it is usually necessary to
conduct the pilot-scale studies using the same modules that
will be used in the full-scale installation.
 Stabilization
Wastewater effluent that is demineralised with reverse
osmosis will generally require pH and calcium carbonate
adjustment (stabilization) to prevent metallic corrosion, due
to the contact of the dimineralized water with metallic pipes
and equipment.
Corrosion occurs because mineral from the solid is removed
(solubilized) to satisfy the various solubility products.
Demineralized water typically is stabilized by adding lime to
adjust the Langelier Saturation Index (LSI).
LSI pH pH s
Where
pH measured pH in concentrate stream water sample
pH s saturation pH for calcium carbonate
 Chemical Storage
The design of chemical precipitation operations involves not
only the sizing of various unit operations and processes but
also the necessary appurtenances.
Because of the corrosive nature of many of the chemicals
used and the different forms in which they are available,
special attention must be given to the design of chemical
storage, feeding, piping and control systems.
The specific storage facilities required will depend on the
form in which the chemical is available locally.
For small treatment plants the available forms are usually
limited.