WASTEWATER TREATMENT

Dr. Prakash D. Vaidya

V. V. Mariwala Lecturer in Chemical Engineering
Institute of Chemical Technology, Mumbai
Tel.: 022-24145616; Email: pdv@udct.org

Lecture Content

Introduction and basic concepts

Industrial wastewater treatment techniques

Illustrating examples

Part I

Introduction and Basic Concepts

Wastewater
Water, adversely affected in quality by anthropogenic
influence (e.g., sewer outfalls, industrial discharges,

agricultural or urban runoffs), is defined as wastewater

Wastewater Constituents:
Oxygen-demanding wastes, disease-causing agents,
organic compounds, inorganic chemicals and minerals,

plant nutrients, sediments, radioactive susbtances,

thermal discharges and oil
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Wastewater (ctd.)
Wastewater can be classified as
Domestic Wastewater

It is discharged from residential/commercial establishments

Industrial Wastewater
It is discharged from manufacturing plants

Wastewaters are also classified as strong, medium or weak,

depending upon the amounts of physical, chemical and

biological constituents
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Industrial Wastewater
Treatment of following industrial wastewaters is essential:

Chemical
Petrochemical
Textiles
Steel
Paper Making
Food Processing
Coke Ovens

Engineering
Metallurgy
Laundry
Agriculture
Dairy
Tanning
Industrial Oil Production

Industrial Wastewater (ctd.)

Major pollutants in industrial wastewaters are:
ORGANIC
Proteins
Carbohydrates
Fats
Oils
Dyestuffs
Organic acids
Phenols
Detergents
Organo-pesticides

INORGANIC
Acids
Alkalies
Metals
Salts
Phosphates
Nitrates
Sulfides
Cyanides
Minerals
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Wastewater Characteristics

Important wastewater characteristics:

Biochemical Oxygen Demand (BOD)
Chemical Oxygen Demand (COD)
Total Organic carbon (TOC)
Theoretical Oxygen Demand (TOD)

Other important parameters are pH, total solids

(dissolved and suspended), total nitrogen, total
phosphorus, chlorides and total metal content
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Biochemical Oxygen Demand

BOD is the amount of oxygen required by

microorganisms to biologically degrade the waste
It is a direct measure of oxygen requirement and an
indirect measure of biodegradable organic matter
It is expressed in terms of the BOD5 value

Biochemical Oxygen Demand (ctd.)

BOD5 (mg/L) :

.d is dilution factor
.DO is dissolved oxygen

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Biochemical Oxygen Demand (ctd.)

Limitations of BOD Test:
Nitrogenous nutrients may create problems
Toxic materials present in industrial wastewaters may
interfere with the growth of microorganisms
The presence of algae in wastewater may lead to
higher BOD values

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Chemical Oxygen Demand

COD is the amount of oxygen required to chemically

oxidize the wastes
The oxidizing bacteria of the BOD test are replaced
here by a strong oxidizing agent under acidic conditions
It is a measure of the total oxidizable organic material
in the sample

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Chemical Oxygen Demand (ctd.)

CaHbNcOd + (a + b/4 d/2) O2

CO2 + H2O + N2

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Chemical Oxygen Demand (ctd.)

Advantages of COD Test:

Useful for quick estimation of oxygen requirements of

industrial wastewaters
Useful when BOD test is not applicable due to the
presence of toxic substances or low rate of oxidation
BOD / COD ratio gives an indication of the degree of
biotreatability of the waste

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Total Organic Carbon

TOC is based on the oxidation of carbon present in
organic matter to CO2, which is measured by a nondispersive infrared analyzer
Organic Carbon = Total Carbon Inorganic Carbon

TOC value can be quickly estimated when compared to

BOD and COD measurements
An empirical correlation between TOC and COD or
BOD can be developed for a specific plant operation

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Total Organic Carbon (ctd.)

TOC is related to COD through a carbon-oxygen balance:

When the organic material is resistant to dichromate

oxidation,
COD/TOC = 0
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Theoretical Oxygen Demand

TOD of wastewater is calculated as the oxygen

required to oxidize the organics to end products
TOD test measures organic carbon and unoxidized
nitrogen and sulfur
For most organics (except some aromatics),
COD = TOD

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Theoretical Oxygen Demand (ctd.)

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Water Pollution Laws and Standards

Water Pollution Act (1974)

Water (Prevention and Control of Pollution)
Cess Act (1977)

Environmental (Protection) Act, 1986

Environmental (Protection) Rules, 1986

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Part II

Industrial Wastewater Treatment Techniques

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Wastewater Treatment Processes

Physical
e.g., screening, sedimentation, flotation and filtration
Chemical
e.g., precipitation and coagulation
Biological
e.g., activated sludge process and trickling filters
Air Stripping, Carbon Adsorption, Oxidation and
Reduction, Ion Exchange, and Membrane Processes
are of significance too!

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Treatment Processes (ctd.)

Another classification is as follows:

Primary
Removal of suspended solids and floating matter
Secondary (or Biological)
Removal of soluble or colloidal organic matter
Tertiary (or Advanced)
Removal of soluble non-biodegradable organics
(e.g., surfactants) and dissolved inorganic salts

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General Overview

Primary

Physical/
Chemical

Secondary

Biological

Tertiary

Polishing

Filtration/
Adsorption

Disinfection

Sludge Treatment
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General Overview (ctd.)

Raw Wastewater Influent

PRELIMINARY

Preliminary Residuals
A (i.e., grit, rags, etc.)

PRIMARY
Clarifier

SECONDARY
Usually to Landfill

B Primary Sludge

Biological
Treatment
System

Wastewater
Treatment
Residuals

Clarifier
Clarifier

C Secondary Sludge
Biosolids
Processing
and Disposal

(e.g., attached-growth
Suspended-Growth,
Constructed Wetland, etc.)

DISINFECTION

Clean Wastewater Effluent

Discharge to Receiving Waters

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25

Treatment Processes (ctd.)

Criteria for selection of a treatment process:

Wastewater characteristics
(e. g., type of pollutant, biodegradability , toxicity)
Required effluent quality
Costs and availability of land

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Primary Treatment

Primary treatment comprises:

Pretreatment
Sedimentation
Flotation
Neutralization
Coagulation

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Pretreatment
Large floating and suspended solids are removed
STEPS:
Screening
Manual or Mechanical
Contaminants removed during screening are
disposed by burial, incineration and grinding
A communitor may be used instead of the screens
Grit removal
Grit chambers remove inorganic grit (e.g., sand, gravel,
cinders, and pebbles)
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Pretreatment (ctd.)

Equalization

It is done in a mixing basin to level out the hour-tohour variations in flows and concentrations
Equalization basins may be designed to equalize
flow, concentrations or both
Size and type of basin varies with the quantity of
waste and variability of the wastewater stream

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Pretreatment (ctd.)

Equalization Basins:

Qin = Qout

Qin variable

Qout constant

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Pretreatment (ctd.)

Equalization is essential:
To prevent shock loading of biological systems
To provide adequate pH control and minimize chemical
requirement for neutralization
To minimize flow surges to physical-chemical treatment
systems

To distribute waste loads more evenly

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Sedimentation

Settleable solids are removed by gravitational settling

under quiescent conditions
Sludge formed at the bottom of the tank is removed as
underflow, whereas the clear liquid is removed as overflow
Sedimentation may be carried out in rectangular
horizontal flow, circular radial flow or vertical flow basins

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Sedimentation (ctd.)
TYPES:

Discrete settling
Flocculent settling
Zone settling

Flotation may be used instead of sedimentation

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Flotation

TYPES:
Dispersed air flotation
Dissolved air flotation
Without recycle
With recycle

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Flotation (ctd.)

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Oil Separation

Free oil is floated to the surface of a tank and skimmed

off
Emulsions of oily materials are broken (e.g., by
acidification or addition of lime) and they can be separated
by gravity, coagulation or air flotation

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Neutralization

Neutralization of industrial wastes containing acidic or

alkaline materials is essential
e.g., for biological treatment, pH between 6.5 and 8.5 is
essential for optimum biological activity
The degree of neutralization required depends upon the
causticity or acidity present in the waste

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Neutralization (ctd.)

TYPES
Mixing acidic and alkaline waste streams
Neutralization of acid wastes through limestone beds
Mixing acid wastes with lime slurries
Neutralization of alkaline wastes using strong acids

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Coagulation

It is used for the removal of suspended and colloidal

solids
Alum is the most popular coagulant used in wastewater
treatment
Wastes containing emulsified oils can be clarified by
coagulation too

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Secondary Treatment
In secondary treatment, organic substrate is converted
by microorganisms into CO2, H2O and new cells
Types of Microorganisms:
Aerobic (requiring free oxygen)

Anaerobic (not requiring free oxygen)

Facultative (growing with or without oxygen)
Anoxic (using bound oxygen, e.g., from NO3 for
denitrification)

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Aerobic Processes

Biodegradation of organic matter is

achieved by aerobic bacteria
TYPES:
Activated Sludge System
Trickling Filters
Rotating Biological Contactors

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Activated Sludge Process

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Activated Sludge Process (ctd.)

System Constituents:
Aeration tank
Clarifier

The process is reliable, suitable for handling large volumes

of wastewater, and provides a high degree of treatment

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Activated Sludge Process (ctd.)

PROCESS MODIFICATIONS:
Conventional system
Tapered aeration
Step aeration

Complete mix system

Contact stabilization
Pure oxygen system

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Trickling Filters

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Trickling Filters (ctd.)

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Trickling Filters (ctd.)

Waste is sprinkled over a bed packing coated with a
biological slime
Microorganisms convert organics into CO2 and NO3

The system has good adaptability to handle peak shock

loads and is easy to operate

Milk processing, paper mill and pharmaceutical wastes

are among those treated by trickling filters

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TF vs. ASP
Trickling filters
Bacterial growth is fixed on the media
All solids from the settler are wasted
Less sensitive to shock loading
Less effective in removing pathogens
Low operating costs
Activated sludge system
Bacterial growth is suspended as a dispersed floc
Solids from the settler are partially recycled
More sensitive to shock loadings
More effective in removing pathogens
High operating costs
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Rotating Biological Contactors

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Rotating Biological Contactors (ctd.)

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Rotating Biological Contactors (ctd.)

It consists of large-diameter plastic media mounted
on a horizontal shaft in a tank
A 1 to 4 mm layer of slime biomass is developed on
the media
As the contactor rotates, it carries a film of
wastewater through the air, resulting in oxygen and
nutrient transfer
Additional removal occurs as the contactor rotates
through the liquid in the tank

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Biological Processes

Sludge Treatment and Disposal

Concentration gravity thickening and flotation

Digestion aerobic, anaerobic, sludge lagoons
Conditioning chemical addition, heat treatment
Dewatering centrifuging, vacuum filtration, pressure
filtration, drying beds, heat drying

Oxidation incineration, wet air oxidation

Ultimate sludge disposal

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Anaerobic Processes

Anaerobic decomposition involves the breakdown of

organic wastes into gas (CH4 and CO2) in the absence
of oxygen
Anaerobic Processes are used in the treatment of:
Meat packing wastewater
Pharmaceutical wastewater
Beet-sugar wastewater
Paper mill wastewater
Dairy wastewater, food-processing and brewery waste

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Anaerobic Processes (ctd.)

MECHANISM
Carbohydrates
H2O

Fats

H2O

Acetic acid/
Propionic acid
H2O

H2O

Proteins

Methane Bacteria

CH4, CO2

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Anaerobic Processes (ctd.)

Types of Anaerobic Processes:

Anaerobic Contact Process
Anaerobic Filter Process
Up-flow Anaerobic Sludge Blanket (UASB)
Fluidized Bed Reactor
ADI-BVF Process

Factors affecting process operation are temperature,

pH and the presence of toxic metals, ions and
compounds

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Aerobic vs. Anaerobic Processes

Anaerobic processes:
Growth rate is slow
Yield of organisms is less

Removal rate of organics is less

Sludge yield is considerably less
Nutrient requirements are less

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Tertiary Treatment
TERTIARY TREATMENT TECHNIQUES

Filtration
It is usually carried out using beds of porous media such
as sand or coal
A mixed-media filter, graded coarse to fine in the
direction of water flow, may be used too
It comprises fine garnet in the bottom layer, silica sand in
the middle layer and coarser coal in the top layer

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Tertiary Treatment (ctd.)

Chemical Oxidation
Disinfection of wastewater
Breakpoint Chlorination

Examples of chemical oxidants are chlorine and ozone

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Tertiary Treatment
Solvent Extraction
e.g., Benzene is used as a solvent for the extraction
of phenol from wastewater
e.g., Amines are used as extractants for the recovery
of metal cyanides from plating waste streams
Adsorption on Activated Carbon
DuPonts powdered activated carbon process involves
direct addition of adsorbent into aeration tank of activated
sludge system

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Tertiary Treatment (ctd.)

Ion Exchange
Used for removal of water hardness and recovery of
trace metals from industrial wastes
Membrane Separation
Reverse Osmosis
Used for desalting, separation of toxic ions from
plating wastes, concentration of radioactive wastes
Electrodialysis
Advanced Oxidation Processes
Wet Air Oxidation
Fenton Oxidation
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Wet Air Oxidation

It involves sub-critical oxidation of organics and some
oxidizable inorganics in aqueous phase at high
temperatures (150 300 oC) and pressures (0.5 20 MPa)
Organic compounds are oxidized into CO2 and other
innocuous end products; nitrogen is converted into
ammonia, NO3 or elemental nitrogen; halogen and sulfur
are converted into inorganic halides and sulfates

It is suitable for treatment of substances that are resistant

to biological treatment. Energy required for this process is
much less than that required for incineration.

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Wet Air Oxidation (ctd.)

Schematic Diagram
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Wet Air Oxidation (ctd.)

LOPROX Process
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Wet Air Oxidation (ctd.)

Industrial Applications of Wet Oxidation:

Wet oxidation of municipal sewage sludge
Wet oxidation of alcohol distillery waste
Treatment of pulp and paper mill effluent
Treatment of cyanide, cyanate and nitrile wastewater
Regeneration of spent carbon and spent earth
Energy and resource generation
Wet oxidation of phenol-bearing spent caustic

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Fenton Oxidation
Organic substrate is oxidized by H2O2 in presence of
homogeneous iron catalyst
MECHANISM

Advanced Fenton processes are UV-Fenton,

Photo-Fenton, Fenton-Ozonation and FentonBiological Treatment
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Fenton Oxidation (ctd.)

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Part III

Illustrating Examples

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Distillery Waste Treatment Options

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Distillery Waste (ctd.)

Several processes (e.g., aerobic, anaerobic and

physico-chemical) have been used for treatment
Physico-chemical treatment has met with little
success, whereas anaerobic treatment with biogas
recovery is highly effective
An inverse anaerobic fluidization technology, which
enables 85 % COD reduction, is very attractive
according to Sowmeyan and Swaminathan (2008)

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Nitrogenous Organic Pollutants

Industrial waters polluted by nitrogenous organics:

Production of rubber additives (e.g., aniline)
Synthesis of dyes
TNT production
Acetonitrile production

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Nitrogenous Organics (ctd.)

Treatment of toxic nitrogenous organics (e.g., aniline,

nitrobenzene, nitrophenol and piperazine) by following
advanced oxidation processes is promising:
WET AIR OXIDATION
PHOTO-FENTON

UV
OZONATION

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Recent Trends

Wastewater reclamation
e.g., use of treated wastewater for municipal
purposes, recycle and reuse of treated effluents
Zero effluent discharge

Hybrid processes (e.g., MEMWO, SONIWO)

Membrane bioreactors
Rootzone technology

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