Module V

Lecture 1
(1) Boiler feed water

Water is mainly used in boiler for the generation of steam (for industries and power
houses). If excess of impurities are present in boiler feed water, following problems
may occur in boiler.

 scale formation

 sludge formation
 priming
 foaming
 boiler corrosion

Scale and sludge formation in boiler

In boilers, water evaporates continuously and the concentration of the dissolved salts
increases. When their concentration reach saturation point, they are thrown out of
water in the form of precipitates on the inner walls of the boiler. If the precipitate
formed is soft and loose, then it is called sludge. If the precipitate formed is hard, it is
called scale.
Sludge
Sludge is a soft and loose precipitate formed within the boiler. Sludge can be easily
scrapped off. It is formed at the colder portions of the boiler and collects in the areas
where the flow rate is slow.
Disadvantages:

 Sludge are poor conductor of heat, so they tend to waste a portion of heat
generated.

 Excessive sludge formation disturbs the working of the boiler. It settles in the
region of poor water circulation, such as pipe connection, plug opening, thereby
causing choking of the pipes.
Prevention of sludge formation

 By using well softened water

 By ‘Blow down operation’, i.e drawing off a portion of the concentrated water.

Scale
Scales are hard deposits, which stick very firmly to the inner surfaces of the boiler.
Scales are very difficult to remove and are the main source of boiler trouble.
Formation of scales may be due to:
 Decomposition of calcium carbonate

Ca(HCO3)2  CaCO3 (Scale) + H2O + CO2

 Deposition calcium phosphate

CaSO4 is soluble in cold water, but is insoluble in super- heated water.

Hence, CaSO4 gets precipitated as hard scale on the heated portion of the boiler.

 Hydrolysis of magnesium salts

Dissolved magnesium salts undergo hydrolysis at high temperature

inside the boiler forming magnesium hydroxide precipitate.
MgCl2 + 2H2O  Mg(OH)2 (scale) + 2HCl

Disadvantages of scale formation

 Wastage of fuel

 Lowering of boiler safety

 Danger of explosion

 Decrease in efficiency

Removal of scales

 By use of scrapers or wire brush if the scales are loosely adhered

 With the help of scrapper if they are loosely adhered

 By giving thermal shocks

 By adding chemicals

Priming
 When a boiler is steaming rapidly, some particles of the liquid water are carried
along with the steam. This process of wet steam formation is called priming.
Priming is caused by:
 presence of large amount of dissolved solids
 High steam velocities
 Improper boiler design
 sudden increase in steam production rate
Priming can be minimized by:
 fitting mechanical steam purifiers
 avoiding rapid change in steaming rate
 efficient softening and filtration of the boiler feed water
Foaming
Foaming is the production of persistent foam or bubbles in boilers which do not break
easily. Foaming is due to the presence of substances like oils.
Foaming can be avoided by:
 Adding anti-foaming chemicals like castor oil.
 adding compounds like sodium aluminate for removing oil from boiler water
Boiler corrosion
Boiler corrosion is decay of boiler material by a chemical or electrochemical attack by
its environments.
Main reasons for boiler corrosion are:

 Dissolved oxygen (DO): Water can contain up to about 8 ml of DO per liter at

room temperature. DO in water, at high temperature attacks boiler materials.
2Fe + 2H2O + O2 à 2Fe(OH)2
4Fe(OH)2 + O2 à 2[Fe2O3.2H2O] (rust)

 Acids from dissolved salts: Water containing dissolved Mg salt liberates acids
on hydrolysis. The liberated acids reacts with iron (of the boiler), thus producing
corrosion.

 Dissolved CO2:

Dissolved CO2 is a carbonic acid

 CO2 + H2O à H2CO3

It has a slow corrosive effect on the boiler material.

Prevention of scale formation

(1) Internal treatment
An internal treatment is accomplished by adding a proper chemical to boiler water:
(a) to precipitate the scale forming impurities in the form of sludges which can be
removed by blow-down operation.
(b) To convert them into compounds which will stay in dissolved form and thus they
do not cause any harm.
Important internal treatment methods are:
Phosphate conditioning: In high pressure boilers, scale formation can be avoided by
adding sodium phosphate. It reacts with hardness of water forming non-adherent and
easily removable, soft sludge of Ca & Mg phosphates which can be removed by blow
down operation.
3CaCl2 + 2Na3PO4 à Ca3(PO4)2 + 6NaCl

Calgon conditioning: It involves in adding calgon to boiler water. It prevents the

scale & sludge formation by forming soluble complex compound with CaSO4.
Na2[Na4(PO3)6] <--->2Na+ [Na4P6O18]2-
(calgon)
2CaSO4 + [Na4P6O18]2-à [Ca2P6O18]2- + 2Na2SO4

(2) External treatment (Softening of water)

The process of treating water to remove hardness producing ions such as Ca2+, Mg2+
etc. is known as softening of water.
(i) Lime-Soda Process:
In this method, the soluble Ca & Mg salts in water are chemically converted into
insoluble compounds by adding calculated amount of lime [Ca(OH)2] and soda
[Na2CO3].
Reactions:
Mg2+ + Ca(OH)2  Mg(OH)2 + Ca2+
 Ca2+ + Na2CO3  CaCO3 + Na2+

Cold Lime soda process: In this method calculated amount of chemical (lime and
soda) are mixed with water at room temperature. At room temperature precipitate
formed are finely divided so they do not settle and can not be filtered easily. Small
amounts of coagulants (like sodium aluminate, aluminium sulphate etc.) are added,
which gets hydrolysed to flocculent, gelatinous precipitate of aluminum hydroxide
and entrapes the fine precipitates.

NaAlO2 + 2H2O à NaOH + Al(OH)3

Hot lime-soda process: it involves treating water with softening chemicals at a temp
of 80-150 deg C. Since hot process is operated at a temp nearer to boiling point of the
solution, so
(a) reaction proceeds faster
(b) the softening capacity of hot process is increased
(c) much of the dissolved gases are driven out of the water
(d) viscosity of softened water is lower, so filtration becomes much easier.
(e) hot lime soda process produces water of lower residual hardness of 15-30 ppm.
(f) Flocculent not required to settle the precipitate formed.
Lecture 2

(ii) Ion exchange processes of water treatment:

(a) Zeolite based method:

Zeolite is hydrated sodium alumino silicate, capable of exchanging reversibly its

sodium ions for hardness producing ions in water.
Zeolite are of two types:
(1) Natural Zeolites
(2) Synthetic Zeolites
Process: For softening of water by zeolite based method, hard water is percolated at a
specified rate through a bed of zeolite kept in a cylinder. The hardness causing ions
are retained by the zeolites (as CaZe and MgZe).

Na2Ze + Ca(HCO3)2  CaZe + 2NaHCO3

Na2Ze + Mg(HCO3)2  MgZe + 2NaHCO3

(Ze: Zeolite)
Advantages:
It removes the hardness almost completely.
The equipment occupies small space.
There is no danger of sludge formation as no impurities are precipitated
It requires less time for softening
Disadvanges
The method only replaces Ca2+ and Mg2+ ion by Na ions and leaves all the
acidic ions (HCO3-, CO32-, ). When such softened water is used in boilers, sodium
bicarbonate decomposes producing CO2 which causes corrosion. While sodium
carbonate hydrolyses to sodium hydroxide causing caustic embritlment.
High turbidity water can not be treated efficiently by this method because fine
impurities gets deposited on the zeolite bed.
Regeneration of Zeolite: The spent zeolite is regenerated by passing brine solution
through it.

CaZe + 2 Na+  Na2Ze + Ca2+

(spent (regenarated
zeolite)

(b) Ion exchange Resin based method

Ion exchange resins are insoluble, cross-linked, long change organic polymers with a
microporous structure and the functional groups attached to the chains are responsible
for ion exchanging properties. Resins containing acidic functional groups are capable
of exchanging their H+ ions with other cations of the water, which comes in their
contact. Similarly, those containing basic functional group are capable of exchanging
their OH- ions with anions of the water sample.
Process:
The hard water is passed through cation exchange column, which removes
all the cations like Ca2+, Mg2+ etc. from it and equivalent amount of H+ ions
are released from this column to water.
2RH+ + Ca2+  R2Ca2+ + 2H+
2RH+ + Mg2+  R2Mg2+ + 2H+
(RH: Cation exchange resin)
Then hard water is passed through anion exchange column where
anions like SO42-, Cl-, etc. are removed. Thus
R’OH- + Cl-  R’Cl- + OH-
(R’OH-: Anion exchange resin)
H+ and OH- ions released get combined to produced water molecule .
H+ + OH-  H2O
Thus water coming out from the exchanges is free from cations and anions.
This ion free water is known as de-ionized water or demineralized water.
Regeneration:
The spent cation exchange resin is regenerated by passing hydrochloric acid solution
through it.
R2Ca2+ + HCl  RH+ + Ca2+
The spent anion exchange resin is regenerated by passing caustic soda solution
through it.
R’Cl- + NaOH  R’OH- + NaCl
Desalination of Brackish water (sea water)
(1) Electro dialysis
The unit consists of electrodes and thin rigid ion-selective membranes which
are permeable to either cation or anion. The anode is placed near the anion
selective membrane while the cathode is placed near the cation selective
membrane. As emf is applied between the two electrodes, the cations migrates
through the cation selective membrane, towards the cathode. On the other hand,
the anions pass through the anion selective membrane, towards anode. The net
effect is depletion of ions in the central compartment and their increase in the
side compartments.
Periodically, desalinated water is tapped out from the central compartment
while the side compartments yield concentrated brine (to be disposed off back
to sea).The schematic diagram of the setup has been given above.

NOTE: Ion selective membrane refers to specially designed membranes which permit the
flow of only one type of ion through itself. Anion selective membrane is embedded with
positively charged functional group – hence it is permeable only to anions.
Cation selective membranes are embedded with negatively charged functional group
hence permeable only to cations.
(2) Reverse Osmosis

Osmosis is the phenomenon by virtue of which - When two solutions of different

concentration are separated by a semi-permeable membrane, solvent flow takes place
from the solution of low concentration to that of high concentration, until the
concentration in both sides becomes equal. However, if a pressure greater than the
osmotic pressure is applied on the concentrated solution side, the flow of solvent
reverses i.e. it gets forced to flows from concentrated solution to dilute solution, via
the membrane. This phenomenon is referred as Reverse Osmosis.
Reverse osmosis is effectively used in desalination of seawater, using cellulose
acetate/ polymethyl acrylate/polyamide polymer films as the semipermiable
membrane. The schematic representation of a ‘reverse osmosis’ based desalination
unit has been shown above.

Lecture 3
 (1) Biochemical Oxygen Demand (BOD):
The amount of oxygen required by the microorganisms to oxidize organic wastes
aerobically is called BOD.

Organic matter + O2  CO2 + H2O + New cells+ stable products

(NO3, PO4, SO4,…)

Five day BOD test (BOD5)

The BOD5 test is the total amount of oxygen consumed by micro-organisms during
the first five days of biodegradation. It is also called unseeded BOD5 test.
BOD5 of a diluted sample is given by:
BOD5 = (DOi – DOf)/P
Where, DOi : is the initial DO of the diluted waste water
DOf : is the final DO of the diluted water water (5 days later)
P (dilution factor) = volume of waste water/(volume of waste water +
volume of dilution water)
Standard BOD water holds 300 ml. so,
P = (volume of waste water)/300

Seeded BOD test

In this test diluted water is seeded with micro-organism. The BODw ( BOD of the
waste water alone ) can be determine as follows:

BODmVm = BODwVw + BODdVd -----(1)

where;

BODm : BOD of the mixture(waste water + seeded dilution water)

BODw :BOD of the waste water
BODd :BOD of the seeded dilution water alone
Vw : Volume of waste water
Vd :Volume of seeded dilution water
Vm: Volume of the mixture

Let P = fraction of the mixture of waste water = Vw/Vm

1 – p = fraction of the mixture of seeded dil. Water = Vd/Vm
Rearranging eq (1);
BODw = BODm (Vm/Vw) – BODd (Vd/Vw x Vm/Vm) --------(2)
BODw = BODm / (Vw/Vm) – BODd(Vd/Vm) / (Vw/Vm) ------(3)

Substituting the values of P & (P – I) in eq (3);

BODw = (BODm – BODd ( 1- P)) / P

Since BODm = DOi – DOf & BODd = Bi – Bf
Where Bi = Initial DO of seeded dilution water
Bf = Final DO of seede dilution water

Final expression for the BOD of the waste is as follows;

BODw = (( DOi – DOf ) – (Bi – Bf) (I – P ))/ P

BOD is divided into 2 parts:

(1) Carboneous oxygen demand ( CBOD )

The oxygen needed to oxidize organic carbon to CO 2 is called carboneous oxygen
demand.

(2) Nitrogenous oxygen demand ( NBOD )

The oxygen needed to convert ammonia to nitrate is called nitrogenous oxygen
demand.
When living things die off or excrete waste products, the nitrogen that was tied to
complex organic molecules is converted to ammonia by bacteria & fungi. Then in
aerobic environment following reaction takes place:
Thus nitrification exerts its own oxygen demand.

(2) Chemical oxygen demand (COD )

COD is defined as the amount of oxygen consumed under specified conditions in the
oxidation of organic matter present in a given sample of water. This test is widely
used to measure the organic strength of domestic and industrial waste-waters. In COD
test, the sample is subjected to chemical oxidation with potassium dichromate
(k2Cr2O7) which is a strong chemical oxidising agent.
The main difference between BOD & COD test is that while BOD determines
compounds that can be biologically oxidised, COD measures those substances which
can be chemically oxidised.
Advantages:
 Due to rapid determination, COD is very important parameter in management
and design of the treatment plants.
 COD values can characterize the degree of pollution and self – purification of
various waters.

Limitations of COD

 The main disadvantage of this method is that most organic compounds are
only partially oxidized.
 COD test does not differentiate between bio-inert and bio-degradable
materials.
 Some organic materials like benzene, pyridine, and few other cyclic organic
compounds do not get oxidized by this method.

Method of COD determination:

The method is based on the chemical oxidation of the organic matter of the water
sample, generally by potassium dichromate in presence of a catalyst (silver sulphate),

in 50% H2SO4.

3{CH2O} + 16H+ + 2Cr2O72- 4 Cr 3++ 3CO2 + 11 H2O

The amount of unreacted Cr2O72- is then determined by titration against Standard

mohr’s salt solution. Ag2SO4 catalyses the oxidation of straight chain aliphatic
compounds, aeromatic Hydrocarbons and pyridine. HgSO4 ties up with Cl- as soluble
complex and prevents its interference.
LECTURE 4 & 5
Sewage treatment
(1) Composition: Municipal wastewater is 99.99% water. The characteristics of the
remaining portion vary somewhat from city to city with variation primarily dependent
on inputs from industrial facilities that mix with the somewhat predictable residential
Flows. Given the limitless combination of chemicals found in wastewater, it is too
difficult to list them individually. Instead, they are often classified onto the following
general catagories:
(1) Organic wastes (measured as BOD & COD)
(2) Total Solids (TS) which is further classified into Total suspended solids (TSS) and
Total dissolved solids (TDS). i.e. TS=TDS + TSS
(3) Total Kjeldahl nitrogen (TKN)
(4) Total Phosphorus (as p)
Aerobic vs. Anaerobic treatment
Wastewater is treated by aerobic treatment while the sludge generated in the process
is treated by anaerobic treatment.
Anaerobic digestion is slower than aerobic digestion, but has the advantage that only a
small percentage of wastes are converted into new bacterial cells. Instead, most of the
organics gets converted into carbon-di-oxide and methane gas.
Waste Water Treatment Processes
Treatment processes are generally classified according to the water
quality they are expected to produce. These processes include:
 Primary treatment- removes identifiable suspended solids and floating
matter.

 Secondary (biological) treatment- organic matter that is soluble or in

colloidal form is removed (by biological oxidation), thus drastically
reducing the BOD.
When properly designed and operated, secondary treatment plants
removes 90% of the BOD.

 Advance waste treatment- involve physical, chemical or biological

processes or their various combination depending on the impurities to be
removed.
Primary Treatment
Screening: removes large floating objects that may damage the pumps or clog the
small pipe. A device called comminuter is used to grind coarse material into small
pieces.

After screening the waste water passes into a grit chamber, where it is held for few
minutes. Grit chambers are long chambers which allow settling of grit materials. Grit
chambers are provided to protect pumps from abrasion and to reduce the formation of
heavy deposits in pipes.

In the primary sedimentation stage, sewage flows through large tanks, commonly
called "primary clarifiers" or "primary sedimentation tanks". The tanks are large
enough that sludge can settle and floating material such as grease and oils can rise to
the surface and be skimmed off. The main purpose of the primary sedimentation stage
is to produce both a generally homogeneous liquid capable of being treated
biologically and a sludge that can be separately treated or processed. Primary settling
tanks are usually equipped with mechanically driven scrapers that continually drive
the collected sludge towards a hopper in the base of the tank from where it can be
pumped to further sludge treatment stages
Secondary Treatment
Secondary treatment is designed to substantially degrade the biological content of
the sewage such as are derived from human waste, food waste, soaps and detergent.
The majority of municipal plants treat the settled sewage liquor using aerobic
biological processes. For this to be effective, the biota require both oxygen and a
substrate on which to live. There are a number of ways in which this is done. The
prominent ones are:
(1) Trickling filters
(2) Rotating Biological Contractor (RBC)
(3) Activated Sludge process
Trickling Filters

It consists of a rotating distribution arm that sprays liquid waste water over a circular
bed of rocks (fist size) or other coarse materials. The spaces between the rocks allow
air to circulate to maintain aerobic condition. Here there is no actual filtering so it is
named as trickling filter. Instead, the individual rocks in the bed are covered by a
layer of biological slime that adsorbs and consumes (aerobically) the wastes trickling
through the bed. The slime consists of bacteria but it may also include fungi, algae,
worms and snails. The accumulating slime periodically slides off individual rocks and
is collected at the bottom of the filter along with the treated waste water which is then
passed on to the secondary settling tank where it is removed.
Plastic media are becoming popular as a replacement for rocks.

Rotating Biological Contractor (RBC)

It consists of a series of closely spaced, circular, plastic disks (3.6 m in diameter)

attached to a rotating horizontal shaft. The bottom (40%) of each disk is submerged in
a tank containing the waste water to be treated. The biomass film that grows on the
surface of the disk moves into and out of the waste water as the RBS rotates. When
the micro-organisms are submerged in the waste water they adsorb organics and when
they rotate out they are supplied with the need oxygen.

Activated Sludge process

Activated sludge is a process in sewage treatment in which air or oxygen is forced
into sewage liquor to develop a biological floc which reduces the organic content of
the sewage. In all activated sludge plants, once the sewage has received sufficient
treatment, excess mixed liquor is discharged into settling tanks and the supernatant is
run off to undergo further treatment before discharge. Part of the settled material
mostly bacterial masses (sludge) is returned to the head of the aeration system to re-
seed the new sewage entering the tank. The remaining sludge is further treated prior
to disposal.
Activated Sludge process removes the organic matter by two processes:
(1) By oxidation of organic matter to provide energy for the metabolism of the
microorganisms.
(2) Synthesis incorporation of the organic matter into the cell mass.
Advanced biological system
Oxidation Ponds
Oxidation ponds are large shallow ponds, 1-2 m deep where raw or partially treated
sewage is decomposed by microrganisms. Decomposition mostly taking place near
the surface is aerobic and near the bottom is anaerobic.
Ponds having both aerobic & anaerobic condition are called facultative
ponds.

Advantages:

• Simplicity in operation

• Low cost
 Disadvantages

• Odour problems

• Extensive land area requirements

• Adverse effects on these ponds performance due to seasonal weather changes.

Advance waste treatment (Tertiary treatment)

(1) Nitrogen removal
When living things die off or excrete waste products, the nitrogen that
was tied to complex organic molecules is converted to NH3 by bacteria.
In aerobic environment (nitrification process)

2NH3 + 3O2 à 2NO2- + 2H+ +2H2O

2NO2- +O2 à 2NO3-

The second phase is anerobic denitrification

2NO3- + organic matterà N2 + CO2 + H2O

This process gives harmless elemental nitrogen gas. The energy
to drive this reaction comes from organic matter. Since denitrification process occurs
after waste treatment , so additional source must be provided.
(2) Phosphorus removal
Removal of phosphorus can reduce eutrophic problem. Phosphates can be removed by
adding a coagulant, usually alum [Al2(SO4)3] or lime [Ca (OH)2]

Al2(SO4)3 + 2PO43- ------->2AlPO4+3SO42-

Sludge treatment (anaerobic digestion)

The quantity of sludge produced may be as high as 2% of the original volume of
wastewater, depending somewhat on the treatment process being used. Since sludge
in turn can be as much as 97% water and since the cost of disposal is related to
volume of sludge being processed, one prime goal of sludge treatment is to separate
as much water from the solids as possible. The other goal is to stabilize the solids so
that they are no longer objectionable or environmentally damaging. The traditional
method of sludge processing utilizes anaerobic digestion i.e. it depends on bacteria
that thrives in absence of oxygen. The complex digestion process can be summarized
as:
Acid - forming Methane-forming
bacteria bacteria
complex organics Organic acids CH4, CO2 and
other end products

The gas produced in the digester is about 60% methane, which is a valuable fuel. The
digested sludge is still mostly liquid. The solids has been well digested, so there is
little odor. The most popular way of dewatering the sludge is to pump the sludge on
dewatering beds, where evaporation and seepage remove the water. Other methods
include use of vacuum filters, filter presses, centrifuges or incinerators.The digested
and dewatered sludge is potentially useful as soil conditioner, but mostly it is trucked
away and disposed in landfills.