ADSORPTION

ADSORPTION: BASICS

Adsorption can be defined as a process in which atoms or molecules

move from a bulk phase ( ie solid, liquid or gas ) onto a solid or liquid
surface.
 In other words, it is adhesion of atoms, ions or molecules from a gas
liquid or dissolved solid to a surface.
 Adsorbate – The substance which is adsorbed on the surface.
 Adsorbent – The substance on which surface the adsorbate is adsorbed.
ADSORPTION:PRINCIPLE
 Adsorption is a surface phenomenon & consequence of surface energy.
Surface of liquid or solid is in a state of strain which results in
unbalanced residual force at the surface thereby resulting higher surface
energy.
 The surface of liquids/solids always have a tendency to attract & retain
the molecular species with which it comes in contact. This phenomenon
is known as adsorption.
TYPES OF ADSORPTION

Types of Adsorption Characteristics

Physical Adsorption (Physisorption) Unselective. Low energy of

adsorption.

Associative Chemical Selective ,strongly dependent on

Adsorption(Chemisorption) both gas & solid surface. Higher
energies of adsorption than those of
physisorption
Dissociative Chemical Selective, strongly dependent on
Adsorption(Chemisorption) both gas & solid surface. Higher
energies of adsorption than those of
physisorption.
FACTORS AFFECTING ADSORPTION

 TEMPERATURE
 PRESSURE
 SURFACE AREA
 ACTIVATION OF SOLID ADSORBENT
 AGITATION
 pH
 CHARACTERISTICS OF ADSORBENT
 DOSE OF ADSORBATE & ADSORBENT
LIST OF COMMERCIAL ADSORBENTS

 ACTIVATED CARBON
 SILICA GEL
 ACTIVATED ALUMINA
 SYNTHETIC ZEOLITE
 CLAY
 POLYMERS & RESINS
 ADSORPTION ISOTHERM & ITS TYPES
Adsortion isotherm is a Mathematical Model or Functional
Expression to Depict the Distribution of Solute Between the Solid
& Liquid Phase at Equilibrium at a Constant Fixed Temperature.

Types of Adsorption Isotherms :

• Langmuir Isotherm
• Freundlich Isotherm
LANGMUIR ISOTHERM: BASED ON CERTAIN
ASSUMPTIONS:-
• Each surface site can be singly occupied.
• There are no lateral interactions between adsorbed species.
• The enthalpy of adsorption is independent of surface coverage.
• The energy of adsorption is constant thus creating homogeneity
of energy on the surface.
FREUNDLICH ISOTHERM:BASED ON TWO FACTORS:-
The lateral interaction between the adsorbed molecules.
The energetic surface heterogeneity.
Equation of it- qe =Kf(Ce)^(1/2)
Where Kf & n are empirical constant and the Freundlich constant
“n” denotes the degree of favourability of adsorption
WASTE WATER TREATMENT TECHNIQUES

Ion-Exchange
 Nanofiltration


Adsorption:-
 Electrodialysis


Activated Carbon adsorbents

 Coagulation & Flocculation


Carbon nanotubes adsorbents

 Flotation


Low-cost adsorbents
 Electrochemical treatment


Bioadsorbents


Membrane Filtration:-


Ultrafiltration


Reverse Osmosis

APPLICATIONS OF ADSORPTION

• Effective in heterogeneous catalysis.

• Effective in removing coloring material.
• Effective as ion exchange resins.
• Used as adsorption indicators.
• Used in gas masks.
• Used in dyeing of cloth.
• Used as de-humidizers.
SCOPE OF ADSORPTION
 Adsorption is now recognized as an effective and economic
method for heavy metal & organic pollutants from water
&wastewater treatment.
 The adsorption process offers flexibility in design and
operation and in many cases will produce high-quality treated
effluent. In addition, because adsorption is sometimes
reversible, adsorbents can be regenerated by suitable
desorption process.
 Certain techniques like coagulation, filtration with coagulation,
precipitation, ozonation, adsorption, ion exchange, reverse
osmosis and advanced oxidation processes have been used for
the removal of organic pollutants from polluted water and
wastewater.
 These methods have been found to be limited, since they often
involve high capital and operational costs.
On the other hand ion exchange and reverse osmosis are
more attractive processes because the pollutant values can
be recovered along with their removal from the effluents.

Reverse osmosis, ion exchange and advanced oxidation

processes do not seem to be economically feasible because of
their relatively high investment and operational cost.

Among the possible techniques for water treatments, the

adsorption process by solid adsorbents shows potential as one
of the most efficient methods for the treatment and removal of
organic contaminants in wastewater treatment.
Adsorption has advantages over the other methods
because of simple design and can involve low investment
in term of both initial cost and land required.
 The adsorption process is widely used for treatment of
industrial wastewater from organic and inorganic
pollutants and meet the great attention from the
researchers.
Adsorption has advantages over the other methods because
of simple design and can involve low investment in term of
both initial cost and land required.
The adsorption process is widely used for treatment of
industrial wastewater from organic and inorganic pollutants
and meet the great attention from the researchers.
THANK YOU
 Removal of
dissolved solids
 Types of dissolved solids
• The dissolved solids are of both organic and inorganic types. A
number of methods have been investigated for the removal of
inorganic constituents from waste water. Four methods which are
finding wide application in advanced waste treatment are

• 1. Ion-exchange,

• 2. Electrodialysis and

• 3. Reverse osmosis and 4. Evaporation

• For the removal of soluble organics from waste water the
most commonly used method is adsorption on activated
carbon.
• Solvent extraction is also used to recover certain organic
chemicals like phenol an d amines from industrial waste
waters.
PART-I
REMOVAL OF INORGANIC SOLIDS
1. Evaporation

• “Evaporation” is a process of bringing wastewater to its

boiling point and vaporizing pure water.
• The vapor is either used for power production, condensed
and used for heating, or simply wasted to the surrounding
atmosphere.
• The mineral solids concentrate in the residue may be
sufficiently concentrated for the solids either to be reusable in
the production cycle or to be disposed easily.
• This method of disposal is used for radioactive wastes, and
paper mills have for a long time been evaporating their sulfate
cooking liquors to a degree where they may be returned to the
cookers for reuse
2. Ion exchange

• This technique has been used extensively to remove

hardness, and iron and manganese salts in drinking
water supplies.
• It has also been used selectively to remove specific
impurities and to recover valuable trace metals like
chromium, nickel, copper, lead and cadmium from
industrial waste discharges.
 2R-NA + Ca(HCO3)2 -> R2CA + 2NaHCO3
Sodium Calcium
Calcium Sodium
Ion Ion
+ Bicarbonate -> + Bicarbonate
Exchange Exchange
in Water in Water
Resin Resin

Fully charged Ion exchanged

resin resin
• The process takes advantage of the ability of certain natural
and synthetic materials to exchange one of their ions.
• A number of naturally occuring minerals have ion exchange
properties.
• Among them the notable ones are aluminum silicate minerals,
which are called zeolites.
• Synthetic zeolites have been prepared using solutions of
sodium silicate and sodium aluminate.
 Hard water
Resin is
flows over Ion Counter-flow
exhausted.
Exchange regeneration
Hardness
media. of Resin with Resin is
minerals
Resin is Hardness Brine fully
are
fully mineral Ions solution. charged
passing by
charged. are Hardness again ready
the Resin.
exchanged for Regenerati
minerals are for use.
on process driven off the
Resin.
is needed.
 Membrane
technologies
Difference between
Osmosis and RO
3. Reverse Osmosis
• Reverse osmosis (RO) is a membrane- technology filtration method
that removes many types of large molecules and ions from solutions
by applying pressure to the solution when it is on one side of a
selective membrane.
• The result is that the solute is retained on the pressurized side of the
membrane and the pure solvent is allowed to pass to the other side. To
be "selective," this membrane should not allow large molecules or
ions through the pores (holes), but should allow smaller components
of the solution (such as the solvent) to pass freely.
• Commonly used membrane is Cellulose Acetate
• Pre-treatment of wastewater is needed to avoid membrane
fouling.
• High COD and BOD can also affect membrane.
• Flushes away impurities and does not collect them.
• It can remove almost everything. It allows only water
(H2O) to pass
• Very efficient but Cost is high
RO PLANT
RO MEMBRANE
 Applications of RO
• Applications include treatment and recycle of wastewaters generated
from metal finishing and plating operations; printed circuit board
and semiconductor manufacturing (treatment and recycle of rinse
waters used in electroplating processes); automotive manufacturing
(treatment and recycle of water used for cleaning and painting); food
and
• beverage (concentration of wastewater for reuse and reduction of
BOD prior to discharge); groundwater and landfill leachate (removal
of salts and heavy metals prior to discharge).
 4. Electrodialysis

• Electrodialysis is an electrochemical process whereby electrically

charged particles, ions, are transported from a raw solution
(retentate, diluate) into a more concentrated solution (permeate,
concentrate) through ion-selective membranes by applying an
electric field.
• When a salt solution is under the influence of an electric field, as
is the case in an electrodialysis module, the charge carriers in the
solution come into motion.
• This means that the negatively charged anions migrate towards
the anode and the positively charged cations towards the cathode.
• In order to separate salts from a solution, ion-selective
membranes, through which only one type of ion can permeate in
an ideal case, are arranged in the solution perpendicular to the
electric field.
• Thus negatively charged particles (anions) can pass through an
anion exchange membrane on their way to the anode but are
selectively retained by the upstream cation exchange membrane.
• This separation stage results in a concentration of electrolytes in
the so- called concentrate loop and a depletion of charge carriers
in the so-called diluate loop.
 Applications

• Nitrogen removal from drinking water (nitrate,

ammonium)
• Desalination of organic substances
• Concentration of salts, acids and bases
• PART-II
REMOVAL ORGANIC DISSOLVED SOLIDS
• Some of the methods used are:
(1) lagooning in oxidation ponds;
(2) activated-sludge treatment;
(3) high-rate aerobic treatment (total oxidation);
(4) trickling filtration;
(5) spray irrigation;
(6) wet combustion;
(7) anaerobic digestion
(8) subsurface disposal; and
(9) the Bio-Disc system (RBC).
(10) Adsorption
 Adsorption

• One of the most commonly used techniques for removing organics

involves the process of adsorption, which is the physical adhesion of
chemicals on to the surface of the solid.
• The effectiveness of the adsorbent is directly related to the amount of
surface area available to attract the particles of contaminant.
• The most commonly used adsorbent is a very porous matrix of
granular activated carbon, which has an enormous surface area (~
1000 m2/g).
• Adsorption on activated carbon is perhaps the most economical and
technically attractive method available for removing soluble organics
such as phenols, chlorinated hydrocarbons, surfactants, and colour
and odour producing substances from waste water.
adsorbate: material being adsorbed.
Adsorbent:material doing the adsorbing. (examples are activated carbon or
ion exchange resin).
Generally some combination of physical and chemical adsorption is
responsible for activated carbon adsorption in water and wastewater.
Physical adsorption:

• Van der Waals attraction between adsorbate and adsorbent.

• The attraction is not fixed to a specific site and the adsorbate is
relatively free to move on the surface.
• This is relatively weak, reversible, adsorption capable of multilayer
adsorption.
 Chemical adsorption:

• Some degree of chemical bonding between adsorbate and adsorbent

characterized by strong attractiveness. Adsorbed molecules are not
free to move on the surface.
• There is a high degree of specificity and typically a monolayer is
formed.
• The process is seldom reversible.
SECONDARY WASTEWATER
TREATMENT
CONTENT :-

• History
• Introduction
• Sewage treatment generally involves three stages
• List of alternative secondary treatment methods
Activated sludge
Aerated lagoon
Aerobic granulation IV.Constructed wetland

• V. Membrane bioreactor VI.Rotating biological contactor

• VII.Trickling filter
 HISTORY
• Basic sewer systems were used for waste removal in ancient Mesopotamia , where vertical
shafts carried the waste away into cesspools. Similar systems existed in the Indus Valley
civilization in modern day India and in Ancient Crete and Greece.
• In the Middle Ages the sewer systems built by the Romans fell into disuse and waste was
collected into cesspools that were periodically emptied by workers known as 'rakers' who would
often sell it as fertilizer to farmers outside the city.
• Modern sewage systems were first built in the mid-nineteenth century as a reaction to the
exacerbation of sanitary conditions brought on by heavy industrialization and urbanization.
• Sewage treatment generally involves three stages
Primary
Secondary
Tertiary Treatment
 INTRODUCTION
• Secondary treatment is designed to substantially degrade the biological content of the sewage
which are derived from human waste, food waste, soaps and detergent.

• Secondary wastewater treatment is a biological processdone digestion which include

processes such as either by aerobic trickling filters, RBC, aerobic granulation or anaerobic
processes such as constructed wetlands, aerated lagoon and membrane bio reactor.
AEROBIC DIGESTION ANEROBIC DIGESTION

• ACTIVATED SLUDGE • Constructed Wetland

• TRICKLING FILTER • Aerated lagoon

• ROTATATING BIOLOGICAL • Membrane Bioreactor

CONTACTOR

• AEROBIC GRANULATION
Some secondary treatment methods include a secondary clarifier to
settle out and separate biological floc or filter material grown in the
secondary treatment bioreactor.

List of alternative secondary treatment methods :

• Activated Sludge
• Aerated Lagoon
• Aerobic Granulation
• Constructed Wetland
• Membrane Bioreactor
• Rotating Biological contactor
• Trickling Filter
 ACTIVATED SLUDGE
• Activated sludge is a process for
treating sewage and industrial
wastewaters using air and a
biological floc composed of
bacteria and protozoa.
 AERATED LAGOON
• An aerated lagoon or aerated basin is a holding
and/or treatment pond provided with
artificial aeration to promote the biological
oxidation of waste waters.
• There are many other biological processes for
treatment of wastewaters, for
example activated sludge, trickling
filters, rotating biological
contactors and biofilters.
• They all have in common the use
of oxygen (or air) and microbial action to
biotreat the pollutants in wastewaters.
 Aerobic Granulation
• The biological treatment of wastewater in
the sewage treatment plant is often
accomplished using conventional activated
sludge systems.
• These systems generally require large surface
areas for treatment and biomass separation
units due to the generally poor settling
properties of the sludge.
• In recent years, new technologies have been
developed to improve settlability. The use
of aerobic granular sludge technology is one
of them.
• STABILITY AND FLEXIBILITY • REQUIRE LARGE AREA

• LOW ENERGY REQUIREMENTS • DEAL WITH LARGE NUMBER

OF CONVERSION
• REDUCED FOOTPRINT PROCESSES

• GOOD BIOMASS RETENTION • REQUIRE SEPRATE TANK

FOR CLEAN EFFLUENT
• PRESENCE OF AEROBIC AND
ANOXIC ZONES INSIDE THE • SLUDGES FROM MUNICIPAL
GRANULES. WASTEWATER TREATMENT
PLANT NEED DIFFERENT
• REDUCED INVSTMENT AND STEPS TO DEWATER
OPERATIONAL COST BEFORE PROCESSED
CONSTRUCTED WETLAND
• A constructed wetland is an
artificial wetland created as a new or
restored habitat for native and
migratory wildlife, for
anthropogenic discharge.

• Natural wetlands act as a bio filter,

removing sediments and pollutants suc
h as heavy metals from the water.

• Constructed wetlands can be designed

to emulate these features.
 • REQUIRE LARGE LAND AREA
• RELATIVELY INEXPENSIVE TO
CONSTRUCT AND OPERATE • EXPOSE THE ODOR OF THE WATER
STREAM IF INPROPER DESIGH
• EFFECTIVE ,RELIABLE ND
ECOLOGICALLY SOUND • BIOLOGICAL PROCESSES ARE NOT
WELL UNDERSTOOD
• TOLERATE BOTH GREAT AND SMALL
VOLUMES OF WATER • NUTRIENT REMOVAL TAKE PLACE
MAINLY DURING THE GROWING
• INCORPORATE PRODUCTIVE USES SEASONS

• AESTHETICALLY PLEASING AND • ORGANISM DIE IN WATER AND

PROVIDE HABITAT FOR WILDLIFE RELEASE THERE NUTRIENT IN
SYSTEM
MEMBRANE BIOREACTOR
• Membrane bioreactor (MBR) is the
combination of a membrane
process like microfiltration or ultrafil
tration with a suspended
growth bioreactor.

• It is widely used for municipal and

industrial wastewater treatment
with plant sizes up to
80,000 population equivalent (i.e. 48
million litres per day).
• Compact • Aeration limitations

• High effluent quality • Stress on sludge in external

MBR
• High volumetric load
possible • Membrane pollution

• High rate of degradation • Cost price

• Possible to convert from

existing conventional
active sludge purification
ROTATING BIOLOGICAL CONTACTOR
• A rotating biological contactor or RBC is a
biological treatment process used in the
treatment of wastewater
following primary treatment.

• The primary treatment process removes

the grit and other solids through a
screening process followed by a period of
settlement.
 TRICKLING FILTERS
• Trickling filters enable organic material in
the wastewater to be adsorbed by a
population of microorganisms (aerobic,
anaerobic, and facultative bacteria; fungi;
algae; and protozoa) attached to the
medium as a biological film or slime layer.

• The organic material is then degraded by the

aerobic microorganisms in the outer part of
the slime layer.
• The sewage slowly moves through the
porous bed and the effluent is collected
at the bottom.
• As the sewage drains through the
porous bed, this microbial community
absorbs and breaks down dissolved
organic nutrients in the sewage; this
reduces the BOD.
• The sewage may need to be re
circulated several times through the
filter in order to reduce the BOD
sufficiently.
• Simple, reliable, biological • Additional treatment
process may be needed to
meet more stringent
• Low power requirement discharge standards.

• Moderate level of skill and • Vector and odour

technical expertise needed problems.
to manage and operate the
system. • Requires regular
operator attention.
 TERTIARY TREATMENT
• After the secondary treatment the treated effluent
is sent for tertiary treatment processes.

• After which water is discharged into a natural

source such as river for further purification by
natural processes.
 FACTS
• Asia’s Largest STP is at Bharwara
situated at outskirts of Lucknow Uttar
Pradesh.

• It treats 340 million litres of the city’s

400 million of discharge each day.
• Stickney Water Reclamation Plant
in Chicago.
• Treats 5.44 Billion litres of water
a day for 2.4 million residents.
• Deer Island STP in
Boston produces 3mv of
electricity using
methane evolved from
the digester.
• It also uses the sludge as
fertilizers and produces
75 tons of fertilizer
each day.
• Bailonggan Waste Water
Treatment plant in China.
Treats 528 million gallons
of water each day.
Equalization Tank in Treatment
Process
 Equalization

Equalization is the operation aimed at eliminating or

minimizing the problems associated with fluctuations in
wastewater flow and characteristics.
Basic operation schemes for equalization
tanks
Objective of Using Equalization Basins
• Minimize or control fluctuations in
wastewater characteristics and flowrate.

• Size and type of equalization basin varies with:

- Quantity of waste
- Variability of the wastewater stream
 Purpose of using equalization for
industrial treatment facilities
• Dampening of organic fluctuations  prevent
shock loading of biological systems
• pH control  Minimize chemical
requirements for neutralization
• Minimize flow surges to physical – chemical
treatment. Permit chemical feed rates
compatible with feeding equipment
 Purpose of using equalization for
industrial treatment facilities
• Provide continuous feed to biological system
(even when the factory is not operating)
• Controlled discharge of wastes to municipal
system. Distribute waste loads evenly.
• Prevent high concentrations of toxic materials
from entering the biological treatment plant.
Mixing Requirements for Equaliztaion
Tanks
• Mixing is required for:
- Adequate equalization
- Prevent settlement of solids
- Oxidation of reducing compounds
- Reduction of BOD by air stripping
(limited)
 Mixing Methods
1. Distribution of inlet flow and baffling
2. Turbine Mixing
3. Diffused air aeration
4. Mechanical aeration
 Mixing Methods
Most common method  Submerged mixers

For readily biodegradable wastes use surface

aerators  0.003 – 0.004 kW /m3

Air requirement for diffused air aeration:

3.5 – 4.0 m3air / m3 waste
Variable volume in the equalization tank 
provide a constant effluent flow

Program effluent pumping rate  Discharge

maximum quantity of waste during periods
of low flow
Organic loading of treatment plant is
maintained constant for 24-h.
Equalization basin equalize
- Flow
or
- Concentration
or
- Both
 Flow equalization
Plot cumulative flow versus time
Determine maximum volume with respect to
constant discharge line
 Concentration Equalization
Equalization basin may be sized to restrict the
dischatge to a maximum concentration
 Equalization volume
• Volume of completely mixed basins used in
treatment can be considered as part of
equalization basin (e.g. Activated sludge)

Example: Total time required for equalization: 16h

Aeration basin: ?
8h
Required equalization: 8 h
 Construction details for
equalization basins
1. Influent should be given to the equalization
basin close to the mixing device to prevent short
circuiting
2. Cleaning system for grease and scum which can
accumulate on the walls should be considered
3. An overflow weir should be installed to
discharge wastewater in case of failure of
pumps
4. Spray nozzles should be installed to break the
foams
 Factors effecting need for equalization

1. Cost of construction 2. Cost saving by

and implementing reducing the effects
effective on downstream
equalization treatment systems
 Flow Equalization Processes
1. ALTERNATING FLOW:
Collects total flow of the effluent for a given
period of time (normally 24 hours) while a
second basin is discharging. Alternative between
filling-discharging. High degree of equalization
by leveling all discharge parameters.
Disadvantage  high construction cost
 Flow Equalization Processes
2. INTERMITTENT FLOW DIVERSION:
Allows any significant variance in stream
parameters to be diverted to an equalization
basin for short durations. Diverted flow is then
bled back into the stream at a controlled rate.
Rate at which the diverted flow is fed back into
main stream depends on:
- volume
- variance of the diverted water  to reduce
downstream effect
 Flow Equalization Processes
3. COMPLETELY MIXED COMBINED FLOW:
Complete mixing of multiple flows combined at
the front end of the facility. Reduce variance in
each stream by thorough mixing with other
flows.
 Flow Equalization Processes
4. COMPLETELY FIXED FLOW:
A large completely mixed holding basin before
wastewater treatment facility. Levels variations
of influent stream parameters and provides a
constant discharge.
• Hourly Wastewater Flow Fluctuation
measured is given. Calculate the
equalization Tank Volume.
Thank You
Neutralization
Basics

 By Definition pH is the measure of free hydrogen activity in

water and can be expressed as :
 pH= -log[H+] and pOH= -log[OH-]
 Measured on a scale of 0-14, solutions with a pH of less than 7.0
are acids while solutions with a pH of greater than 7.0 are bases.
 In very simple terms bases are used to neutralize acids,
while acids are used to neutralize bases.
 The byproducts are normally salts (which may or may not
be soluble) and water.
 Definition

 “Neutralization” can be defined as the treatment of industrial

waste so that it is neither too acidic nor too alkaline for safe
discharge.
 There are several possible reasons that an industry neutralized its
wastewater during the twentieth century and will continue to do
so:
 Reasons……..

 To make industrial waste compatible (in terms of pH) with municipal

sewage when joint treatment is practiced
 To continue reason no. 1; more specifically, to make certain that its
pH does not kill or otherwise inactivate the microorganisms that are
being used to biologically oxidize the organic matter content
 To prevent corrosion of pipelines and equipment leading from the
industry to its ultimate destination
 To comply with effluent standards for excessive acid or alkaline
conditions in sewers or receiving waters.
 To continue reason no. 4; more specifically, to make certain that the
waste discharge pH does not kill fish or otherwise affect other
organisms in receiving waters
 Excessively acid or alkaline wastes should not be discharged into
a receiving stream without treatment.
A stream even in the lowest classification—that is, one classified
for waste disposal and/or navigation—is adversely affected by
low or very high pH values.
 This adverse condition is even more critical when sudden slugs of
acids or alkalis are imposed upon the stream.
 Methods – outline

 There are many acceptable methods for neutralizing over acidity or

over alkalinity of wastewater, such as:
 mixing wastes so that the net effect is a near-neutral pH;
 passing acid wastes through beds of limestone;
 mixing acid wastes with lime slurries adding the proper proportions of
concentrated solutions of caustic soda (NaOH) or soda ash (NA2CO3)
to acid wastes;
 blowing waste boiler-flue to alkaline wastes;
 producing CO2 in alkaline wastes; and
 adding sulfuric acid to alkaline wastes.
 Neutralization Tank Sizing
 Engineers size treatment tanks to allow adequate retention of the
influent for pH measurement and subsequent reagent addition.
 Good engineering practice for pH control requires 15 to 30 minutes
retention time.
 Retention time is calculated by dividing the tank volume by the
average influent flow rate.
Typical pH Neutralization Tank
Piping
pH Neutralization Tank Inlet & Outlet
Location
Part-I

Neutralization of
Acidic wastes
 1. Mixing Wastes
 Mixing of wastes can be accomplished within a single plant
operation or between neighboring industrial plants.
 Acid and alkaline wastes may be produced individually within one
plant and proper mixing of these wastes at appropriate times can
accomplish neutralization, although this usually requires some
storage of each waste to avoid slugs of either acid or alkali
 If one plant produces an alkaline waste that can be pumped
conveniently to an area adjacent to a plant discharging an acid
waste, an economical and feasible system of neutralization
results for each plant.
2. Limestone Treatment for Acid Wastes

 Passing acid wastes through beds of limestone was one of the original
methods of neutralizing them.
 The wastes can be pumped up or down through the bed, depending on the
head available and the cost involved, at a rate of about 1 gallon/min (gpm)
per square foot (ft2) or less. Neutralization proceeds chemically according
to the following typical reaction:
 CaCO3 + H2SO4 → CaSO4 + H2CO3
 Disposing of the used limestone beds can be a serious drawback to
this method of neutralization, because the used limestone must be
replaced by fresh limestone at periodic intervals, with the frequency
of replacement depending on the quantity and quality of acid wastes
being passed through a bed.

 When there are extremely high acid loads, foaming may occur,
especially when organic matter is also present in the waste.
3. Lime-Slurry Treatment for Acid Wastes

 Mixing acid wastes with lime slurries is an effective

procedure for neutralization.
 The reaction is similar to that obtained with limestone beds.
 In this case, however, lime is used up continuously because it
is converted to calcium sulfate and carried out in the waste.
 Though slow acting, lime possesses a high neutralizing
power and its action can be made effective by heating or
oxygenating the mixture.
 It is relatively inexpensive, but in large quantities, cost can be
an important factor.
 Hydrated lime is sometimes difficult to handle, because it tends
to arch, or bridge, over the outlet in storage bins and possesses
poor flow properties, but it is particularly adaptable to
neutralization problems involving small quantities of acid waste,
as it can be stored in bags without special storage facilities.
 4. Caustic-Soda Treatment for Acid
Wastes
 Adding concentrated solutions of caustic soda or sodium carbonate to
acid wastes in the proper proportions results in faster, but more costly,
neutralization.
 Smaller volumes of the agent are required, because these neutralizers are
more powerful than lime or limestone.
 Another advantage is that the reaction products are soluble and do not
increase the hardness of receiving waters.
 Caustic soda is normally bled into the suction side of a pump
discharging acid wastes.
 This method is suitable for small volumes, but for neutralizing
large volumes of acid wastewater, special proportioning
equipment should be provided, as well as a suitably sized
storage tank for the caustic soda with a multiple speed pump for
direct addition of the alkali to the flow of acid wastes.
 When sodium hydroxide is used as a neutralizing agent for carbonic and
sulfuric acid wastes, the following reactions take place:
 Na2CO3 + CO2 + H2O → 2NaHCO3,
 carbonic acid waste
 2NaOH + CO2 → Na2CO3 + H2O;
 NaOH + H2SO4 → NaHSO4 + HOH,
 sulfuric acid waste
 NaHSO4 + NaOH → Na2SO4+ HOH.
 Both these neutralizations take place in two steps and the
end-products depend on the final pH desired.
 For example, one treatment may require a final pH of only 6,
and thus, NaHSO4 would make up the greater part of the
products; another treatment may require a pH of 8, with
most of the product being Na2SO4.
Part-II

Neutralization of
alkaline wastes
1. Using Waste Boiler-Flue Gas

 Blowing waste boiler-flue gas through alkaline wastes is a relatively new

and economical method for neutralizing them. Most of the experimental
work has been carried out on textile.
 Well-burned stack gases contain approximately 14% carbon dioxide.
 CO2 dissolved in wastewater will form carbonic acid (a weak acid), which
in turn reacts with caustic wastes to neutralize the excess alkalinity as
follows:
 CO2 + H2O → H2CO3,
 flue gas wastewater carbonic acid
 H2CO3 + 2NaOH → Na2CO3 + 2H2O, carbonic acid
caustic soda in wastewater soda ash
 H2CO3 + Na2CO3 → 2NaHCO3 + H2O.
 Excess carbonic acid soda ash in waste sodium
bicarbonate in waste
 The equipment required usually consists of a blower placed in the stack, a
gas pipeline to carry the gases to the waste-treatment site, a filter to
remove sulfur and unburned carbon particles from gases, and a gas
diffuser to disperse the stack gases in the wastewater.
 Stack gases evolve hydrogen sulfide from wastewater that contains any
appreciable quantity of sulfur, and this H2S must be burned, absorbed, or
vented positively to the upper atmosphere to prevent nuisance conditions.
2. Carbon Dioxide Treatment for Alkaline
Wastes

 Bottled CO2 is applied to wastewater in much the same way as

compressed air is applied to activated-sludge basins.
 It neutralizes alkaline wastes on the same principle as boiler-feed
gases (i.e., it forms a weak acid [carbonic acid] when dissolved in
water) but with much less operating difficulty.
 The cost may be prohibitive (the financial burden of it is
significantly greater than the benefit ) however, when the
quantity of alkaline wastes is large.
A textile mill producing about 6 million gallons/day of alkaline waste
studied the practical aspects of this method and found that installation
of the equipment necessary to provide bottled CO2 would cost about
$150,000 and the power and fuel to generate it about $275/day—a
considerable expense, even for so large a plant.
3. Sulfuric Acid Treatment for Alkaline Wastes

 The addition of sulfuric acid to alkaline wastes is a fairly

common, but expensive, means of neutralization.
 Storage and feeding equipment requirements are low as
result of its great acidity, but it is difficult to handle
because of its corrosiveness.
 The neutralization reaction that occurs when it is added to
wastewater is as follows:
 2NaOH + H2SO4→ Na2SO4 + 2H2O
 wastewater sulfuric acid as neutralizer resulting neutral salt