Boiler Water Chemistry

Steam Boiler - Training Workshop for Operators & Technicians
Boiler Water chemistry

Introduction
Boiler is a vessel wherein water is heated to convert into steam, with the application of
heat of a burning fuel and/or the hot exhaust gas from some process. The heat potential
available in steam is one of the well-known sources of energy to do mechanical work in
any steam engine. It is essential to maintain uninterrupted flow of steam to the engines
and hence the boiler has to be necessarily fed with adequate supply of water to keep up
a safe level in the drum. In order to ensure long life and trouble free operation of a
boiler it is important to keep the boiler water chemistry under control. Depending upon
the working pressure and temperature of boiler, the quality of Feed Water for the boiler
is to be maintained. However, due to continuous evaporation occurring in boiler, the
concentration of impurities in the boiler goes on increasing. Therefore, it is necessary to
carry out chemical injection in the boiler for forming precipitates of impurities, which are
to be drained out at regular intervals. Due to this regular draining or blow down the
quantity of water in boiler system has got to be continuously made-up by feeding high
purity water which is obtained by appropriate treatment of raw water.
Natural Water:
Though the water, in nature, is available in plenty, it can not be taken for use in a boiler
without a proper chemical treatment. The physical and chemical properties of natural
water, which widely vary, depending upon the source and strata on which it flows,
makes it unsuitable for direct use in a Boiler. The natural water picks up minerals and
salts from the earthen layer, which gets into the solution. Water, therefore, is a mixer of
composite mineral salts in dissolved condition, in varying proportions, composition and
degree. It gets polluted further with multifarious organic and inorganic impurities, due to
disposal of industrial and domestic wastes. Decayed vegetation and marine lives also
contribute to water contamination. Not only the dissolved salts in water, but also the
presence of the coarse and undisolvable substances in suspended form, constituting
mainly of silt and clay matters, generally termed as turbidity, make it unsuitable for
direct use, without any treatment. Natural water, found on earth, contains siliceous
matters, in dissolved as well as in colloidal forms.
Impurities:
Dissolved impurities:
Mainly the dissolved solids found in water are mineral salts. These contaminants in water
exist as salts of calcium, magnesium and sodium, predominantly in the form of bicarbonates, carbonates, chlorides and sulphates. To a lesser extent, potassium and iron
salts are also present. Nitrates and silicates of such substances are also found to a small
degree. Very rarely, Phosphates and a few heavy metals are also found in natural water.
Dissolved Oxygen:
Dissolved oxygen plays significant role in boiler feed water. The oxygen accelerates
corrosion of water tube material. Mainly oxygen is removed only in Deaeretor. Hence
performance of Deaeretor is very important.
Deaerator performance has to be maintained limiting dissolved oxygen to less than 0.01
ppm level. A figure < 0.007 ppm is considered to be very ideal.
Organic Matter:
It is very difficult to eliminate organic matter totally from water. Presence of organic
matter is due to poor pretreatment practice, ineffective D.M. plant performance, resin
leaking or condenser leakage. Quality of raw water at intake point is a deciding factor.
Seasonal changes play a vital role.
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Chlorides:
Presence of chloride in feed water is harmful to the system as whole. Hence it is very
advisable to limit chloride concentration in feed water, keeping in mind, limit prescribed
for boiler water and restriction as per drum pressure ratings. Leak proof condenser and
efficient demineralization are essential prerequisites to avoid contamination due to
chloride. Dosing chemicals fed to the drum can contribute in sizeable proportion to
chloride contamination if the chemicals are not of adequate quality. Very low level
chloride should be tested by selective ion electrode for accuracy.
Suspended and colloidal impurities:
Clay and sand particles constitute a major portion of the suspended matter. Very fine
clay remains in colloidal state. Colloidal suspension of dye material and certain organic
contents, give colour to water, in most cases.
General nature of dissolved contents:
Normally the mineral salts dissolved in water are found to exist in the ionized form.
Generally there is no uniformity in quantity and proportion of such dissolved salts, since
their presence is mainly dependent on the sources of the water. However fair
representations of composition of mineral salts, as widely found in nature are brought
out below:
CATION (Basic Radical)
ANION (Acidic Radical)
Ca
++
(Calcium)
HCO3- (Bicarbonate)
Mg
++
(Magnesium)
CO3--
Na
++
Fe
(Sodium)
(Iron)
Al+++ (Aluminium)
SO4
--
Cl
(Sulphate)
(Chloride)
NO3PO4
(Carbonate)
---
SiO2
(Nitrate)
(Phosphate)
(Silica)
Definitions
pH:
pH is the measure which indicates whether water is acidic or basic in nature. It is
expressed as integer. If pH is 7, the fluid is neither acidic nor alkaline, it is the neutral
state. If the pH is less than 7 it is acidic in nature. If the pH is more than 7 it is alkaline
in nature.
Conductivity:
Conductivity is measured at 25C at local continuous flow sampling point at the down
stream of a strong cation exchanger with a closed cell provision having no access to
atmosphere. The figure is relevant for CO2 free sample only. In case, combined CO2 is
present, conductivity through cation column will be higher in proportion to the CO2
concentration. In such cases correction applied for CO2 will give fairly reliable figures.
Water as feed to boiler:
We have seen that water as available in nature cannot be used directly in boilers for
raising steam. It has to be treated and chemically conditioned to render it fit for use as
feed and make up in the steam generation process. Mechanical and chemical treatments
are the primary steps to make it free from suspended, colloidal and dissolved impurities,
so that it attains perfectly pure status. It is the process of pre-treating and demineralizing the water to make it fit for use in any boiler.
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However, in the actual process of steam generation, it is required to further chemically
treat the water at various stages in order to make it suitable as a feed to a boiler, which
will be non corrosive and protective to various ferrous and non ferrous alloys, deployed
in the design and construction of various equipment. In a nutshell, treatment and further
conditioning of water are necessary for the following objectives:
a) To prevent scaling internals of pressure vessels due to dissolved and suspended
impurities,
b) To prevent corrosion of metallic parts of the boiler, with which water / steam come
in direct contact,
c) To establish protective coating over metallic surfaces to prevent corrosion attack.
d) To avoid salt deposits over turbine blades,
e) To ensure better utilization of heat energy and to improve on efficiency,
In order to ensure to achieve above objectives, following processes of water treatment
are adopted:
1. Pre treatment
2. Demineralization
3. Chemical conditioning
Pretreatment of water:
Clarification:
Pre- treatment to raw water is mainly to make it suitable for further processing of water
by Deionization units. The water entering Demineraliser plant should be free from
suspended, colloidal and organic impurities and the process of pretreatment plays a vital
role in ensuring proper feed input is made to Deionization units. Presence of such
suspended impurities adversely affects the deionization properties of the resins, which
will affect the end quality of Demineralized water. Suspended & colloidal particles are
removed by clarifying the water in a clariflocolator aided by suitable coagulating agents.
Precipitator Clarifier Section:
A precipitator inlet flow control valve controls the raw water inlet flow into the clarified
water basin, through a level controller. A manual by-pass valve is also provided to the
level control valve, so that in case of problem in the level control valve, manual
operation can be done to maintain the level. The precipitator is of a reinforced concrete
construction, in the shape of a truncated conical vessel placed in inverted position, with
a circumferential channel all around the bigger diameter section at the top. The conical
concrete tank consists of a cylindrical tank built internally at the central portion. The
inner cylindrical compartment is known as the flocculating mixing-zone and the outer
compartment, the sedimentation sludge blanket zone. The raw water enters the inner
mixing zone through an open channel from the top and flows downward into the inner
conical tank.
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The precipitator is fitted with a carriage, which can slowly be driven to go round inside
the Clariflocculator. The carriage carries a paddle mechanism, with three or four tiers of
vanes fixed vertically down and hanging from the paddle mechanism. The carriage is
driven by an electric motor and a gear mechanism, with its axis at the center of the
conical tank and the other end of the carriage placed with a wheel over a circular rail,
fitted along the circumference of the conical tank. When the carriage is driven by the
motor it goes round and round the top of the conical tank in a circular motion and the
paddle mechanism stirs well the water in the outer conical zone. Chemicals, Alum and
Lime, solutions are prepared in separate tanks and the prepared solutions are pumped
trough pumps. The chemicals are let into the open channel to get mixed thoroughly with
the raw water flowing along the open channel into the mixing chamber. A water flow
indicating mechanism is fitted in the open channel to indicate the raw water flow.
The precipitator operates on the sludge blanket principle, whereby a bed of sludge
particles is retained in suspension at a predetermined level in the outer cone. The slow
speed agitator ensures thorough mixing of chemicals and raw water and assists in the
completion of precipitator chemical process. The blanket consists of a loose mass of
suspended floc constituting of medium sized particles. These attract and retain finer
particles rising through the blanket, so that, when the water rises above the blanket
zone, it is filtered and is almost clear. Above the blanket zone, some particles of floc
remain but these continue to grow and fall back so that water decanting through
blankets of sludge and rising to the top of the precipitator is almost free from floc and
turbidity. The clear water overflows through the notches and falls into the circumferential
channel and from there through open canal flows into the clarified water tanks.
Continuous spent large floc desludging of the concentrator on the precipitator is carried
out through a pneumatically operated valve which is set to open at regular intervals.
2(two) valves are provided for draining the precipitator.
Ferrous sulphate solution is delivered into the Precipitator by means of twin head
proportional feed 5% solution dosing pump.
(The concentration values for both Lime and Ferrous sulphate dosage for precipitator
change according to raw water quality and will be recommended by the Original
Equipment supplier.)
Chemicals are dosed proportionally to the raw water flow rate by an automatic
proportioning system consisting of a flow recorder control totalizer and low flow alarm,
which regulates the stroke of the ferrous sulphate pump and the swing angle of the lime
dosing device respectively.
The raw water is treated in the precipitator with hydrated lime for removal of temporary
hardness, caused by bicarbonate in Calcium and Magnesium salts. Hydrated lime reacts
chemically with the bicarbonates of Calcium and Magnesium salts in the water, forming a
sludge of calcium carbonate and magnesium oxide, which gets settled down in layers.
Alum, chemically known as Ferrous Sulphate is also added along with lime dosing, in the
clariflocculator to hasten the process of coagulation and assist in settling of the sludge.
Filtration:
Water filtration is the process of separating suspended and colloidal impurities from
water by passage through a porous medium. A bed of granular filter material or media is
used in most plant application.
A filter may be defined simply as a device consisting of a tank, suitable filter media and
necessary piping, valves and controls. Filters are designed for the following:
Gravity flow, with natural head of water above the filter bed and low point of
discharge at the filter bottom, providing the pressure differential needed to move
the water through the filter bed.
Pressure units, which, as their name implies, are operated on line, under service
pressure, filtering the water as it flows the tank on its way to service or storage
Filters are classified in a number of different ways by type or kind of filter medium to
be deployed, such as sand, anthracite coal, activated carbon, fabric or porous
membranes, or, by the direction of flow upflow or downflow. Also, they are sometimes
described hydraulically as the slow rate or rapid rate type. Varied design and process
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techniques are adopted based on the quality and the quantum of the raw water, to be
treated and the quality of the effluent to be achieved. Economy is a vital point to reckon
with. Sand Filters are used for this purpose.
Gravity Filters: Gravity filters are usually employed where large quantities of filtered
water are required. It normally use 8 to 12 feet high tank constructed of steel or
concrete. Concrete tanks are usually rectangular; steel tanks are round or rectangular.
The end of gravity filter runs is usually determined by the head loss or pressure loss
developed across the filter bed, and backwashing is initiated on this basis. Water quality
deterioration (turbidity breakthrough) can also be used.
Pressure Filters: Three basic types of Pressure Filters are: Vertical Downflow,
Horizontal Downflow and Vertical Upflow. Vertical and horizontal downflow pressure filter
units are the work horse of the filtration field and most widely used.
Backwashing: When differential head between inlet and outlet increases, the filters
must be taken out of service and backwashed for removing accumulated dirt and sludge
materials. The filters are nevertheless to be backwashed at least once every operating
day. For back wash the flow direction is reversed that is the inlet is given at the bottom
and water from the top is delivered out to open canal. When the water flows in reverse
direction it carries all the accumulated dirt and sediments and throws out along with the
water. The back washing is to be done until the out flowing water is perfectly clear of all
accumulated sediments.
Chlorine removal:
To avoid algae formation chlorine is dosed into raw water, before the process of
clarification in the clariflocculator. Presence of chlorine is harmful to the Ion Exchange
Resin and it is essential to ensure that even the traces of chlorine are not present in the
clarified and filtered water, before admission to deionizing unit. Hence before admission
to cation vessel, the water is once again filtered treated in a vessel containing a bed of
Activated Carbon. Activated Carbon Bed absorbs left over chlorine and the organic
matters and feeds clear water to the ion exchange vessels.
Demineralization:
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Demineralization is the removal of dissolved ionic impurities that are present in water.
Demineralized water is commonly produced by one or a combination of the following
processes:
Ion exchange
Membrane desalination or RO (Reverse Osmosis)
Thermal desalination
The method selected to produce demineralized water depends on the quality of the
influent water, the required quality of the effluent water, the availability of resources
such as regenerant chemicals, and wastewater treatment and disposal requirements.
The economics of the processes that produce acceptable effluent quality must be
evaluated to determine the most cost-effective method for a specific application.
Ion Exchange Process:
Basically the minerals present in water are in ionized condition. Ion exchange
demineralization therefore is one of the most important and widely applied processes for
the production of high-purity water for power plant services, and it is accomplished using
resins that exchange one ion for another. Cation resins are solid spherical beads with
fixed negatively charged sites and exchangeable positively charged sites. Anion resins
are solid spherical beads that have fixed positively charged sites and exchangeable
negatively charged sites. In their regenerated state for demineralization applications,
cation resins are in the hydrogen form and anion resins are in the hydroxide form. The
reactions of the resin beads with the dissolved impurities in the water are represented by
the following:
Cation resin:
R-H+ + C+ R-C+ + H+
2R-H+ + C2+ R2-C2+ + 2H+
Anion resin:
R+OH- + A- R+A- + OH2R+OH- + A2- R2+A2 + 2OH-
where
R = resin matrix and fixed charge site;
C = cations such as Ca2+, Mg2+, and Na+; and
A = anions such as HCO3-, Cl-, and SO4-2
The hydrogen ions (H+) displaced from the cation resin react with the hydroxide ions
(OH-) displaced form the anion resin. The net effect is the dissolved ions are removed
from the water and replaced by pure water (H2O).
The ion exchange resins are contained in ion exchange pressure vessels. The ion
exchange resin in the vessels is referred to as the resin bed. This process of exchanging
dissolved impurities is cyclic. When a resin bed site is exchanged with a dissolved ion,
the site becomes exhausted and cannot remove other impurities without releasing an
impurity. Exhausted resins must be regenerated to return the resin beads to the original
hydrogen form for cations and hydroxide form for anions before further ion exchange
can take place.
Cation resins are commonly regenerated with a strong acid solution of either sulfuric or
hydrochloric acid. Anion resins are commonly regenerated with a sodium hydroxide
solution. As can be seen from the regeneration reactions listed below, regeneration is
the reverse reaction to the impurity exchange reactions.
Cation resin regeneration:
2R-C+ + H2SO4 2R-H + C2+SO42R2-C2+ + H2SO4 2R-H+ + C2+SO42-
Anion resin regeneration:
R+A- + NaOH R+OH- + Na+AR2+A2- + 2NaOH 2R+OH- + Na2+A2-
Ion Exchange Resins:

Cation resins are commercially available in strong-acid and weak-acid forms. Strong-acid
cation resins can remove all cations in the influent water whereas weak-acid cation
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resins generally are restricted to the removal of hardness associated with carbonate
alkalinity.
Anion resins are commercially available in strong-base and weak-base forms. Strongbase anion resins are capable of removing both weakly dissociated and strongly
dissociated acids. Weak-base anion resins primarily provide removal of the strongly
dissociated acids (such as hydrochloric, sulfuric, and nitric) and have only limited
capability for removal of weakly dissociated acids.
Cation and anion resins have different affinities for the different dissolved ions.
Consequently, the cation and anion resins display a selectivity series for dissolved ions.
Listed below is a representative selectivity series for commonly used strong-acid cation
resins and strong-base anion resins with the ion having the greatest affinity for the resin
at the bottom of the list.
Selectivity of strong-acid cation and strong-base anion resins
Cations
Anions
2+
Calcium (Ca )
Sulfate (SO42-)
Magnesium (Mg2+)
Chloride (Cl-)
Ammonium (NH4+)
Bicarbonate (HCO3-)
Potassium (K )
Silica (exchanges as HSiO3-)
Sodium (Na+)
Hydroxide (OH-)
Hydrogen (H )
Back Wash:
Water is passed upwards in reverse flow through the column and then thrown to drain.
This loosens and cleans the ion exchange material and prevents it from becoming
packed. When the water enters at the bottom the whole bed is loosened and lifted up.
The swollen bed height can be seen through a glass window. The top level of resin bed to
which it has to raise is marked on the glass window. Quantity of back wash water is to
be maintained such that the resin bed is always raised and held at that level marking
through out the back wash process. During back wash air scoring is also given to loosen
the impurities got accumulated in the bed.
Acid wash:
The required amount of hydrochloric acid is injected into the units after diluting it to
required concentration. Proportioning of 30% acid solution into 7% dilution is done
through a water injector. When water flows through the injector it creates vacuum at the
throat and the acid is sucked through line, which is connected to the throat. After the
throat the acid and the water get mixed up thoroughly and the effluent is let out to
sewer canal. Usually the sewer canal consists of a level mark. The acid water mix flow is
always to be maintained to corresponding level mark during acid dosing. The acid
effluent is taken to a neutralizing tank, where the solution can be mixed with required
quantity of bleaching powder or lime soda so increase its PH to +8 and pumped out to
sewage system.
Rinse:
Water is passed downwards through the column. This brings the regenerant into contact
with the whole of the exhausted resin bed. The rinse is continued till excess regenerant
has been removed.
Deaeration (Degasification):
Deaeration is the process of removing dissolved corrosive gases (O2 and CO2) from
water. This process is also called degasification. Dissolved oxygen acts as a depolarizer
and contributes to the corrosion of metal
Whereas Carbon dioxide dissolved in water liberates H+ ions that attack metal
CO2 + H2O H2CO3 H+ + HCO3- (carbonic acid)
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The process of deaeration is most frequently applied in boiler feed water heaters to
protect piping, boilers and condensate equipment from corrosion.
Deaeration is a thermal method where water is heated to bring about degasification,
unlike de-oxygenation where it is carried out mainly by chemical techniques. The three
cardinal principles that must be satisfied in any mechanical deaerator are:
Heating: Water must be heated to full saturation temperature (boiling point),
corresponding to the steam pressure in the unit. Since, theoretically, the solubility of any
gas is zero at the boiling point of the liquid, complete gas removal is not possible unless
the liquid is kept at boiling temperature.
Mechanical agitation: The heated water must be mechanically agitated, by spraying,
cascading over trays, or by atomization, to expose maximum surface contact to the
scrubbing atmosphere, thus permitting complete release and removal of gases.
Complete gas removal: adequate steam must be passed through the water to scrub
out and carry away the gases after release. Extremely low partial gas pressure must be
maintained since Henrys law states that the amount of gas which will dissolve in a liquid
is proportional to the partial gas pressure in the atmosphere contacting the liquid. It is
mandatory that the volume of scrubbing steam be high to produce the low partial gas
pressure, and it is equally mandatory that the conditions prevail through out the
deaeration process.
Deaerator: A deaerator is the apparatus wherein deaeration is carried out. Deaerators
can be classified in accordance with the mode of steam-water distribution in them.
1. Atomizing deaerator
2. Tray-type deaerator
3. Film-type deaerator.
A direct-contact deaerator consists of a deaerator column fitted on the top of the storage
tank.
The deaerator column is a
cylindrical vessel provided with
hollow
(a) Perforated,
horizontal
trays
arranged one above the other.
(b) Water distribution device at the top.
(c) Steam distributor at the bottom.
Feedwater enters the deaerator from the
top and is evenly distributed, by means of
the
distributing
device,
into
the
perforated trays fitted at the bottom.
Water fills the perforations (dia 5-7 mm)
and rains down and comes in contact with
heating steam dissolved into the lower
portion of the deaerator column through
the steam distributor. As a result of heat
exchange between the steam going up
and the feedwater stream flowing down,
the water gets heated up to its boiling
point and the gases (O2, CO2) dissolved in
it are transferred to the gas phase.
These gases together with non-condensing vapour are vented into the atmosphere
through a vent valve or pass into a vent condenser where the steam is condensed and
the O2 and CO2 are vented.
The deaerated water is collected in the storage tank which is fitted with gauge glass,
pressure gauge and hydraulic seal to avoid the formation of high pressure or vacuum in
the deaerator.
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Degasifier: Carbon dioxide can be removed by either vacuum degasification or forced
draft degasification.
A vacuum degasifier is a packed tower in
which the water is sprayed and the gases
are removed to a low level by maintaining
a vacuum in the tower. A schematic
representation of a typical two-stage
vacuum degasifier is given here. A forced
draft degasifier is a packed tower in
which the water is sprayed down the
column and the carbon dioxide is
removed by air that is blown up the
column.
Determination of whether a gasifier is to
be used and the type of degasifier used
depends on the amount of CO2 produced
following cation exchange and the
effluent water quality (dissolved oxygen
content) required. For moderate to large
concentrations of carbon dioxide, it is
more economical to remove the CO2 by
degasification than by anion exchange.
Mixed Bed:
The effluent water from anion exchanger may still have some silica. The water needs to
be polished. Hence the water drawn from DM tank before it is supplied to boiler feed is
passed through mixed bed exchanger. The mixed bed exchanger is similar to Cation or
Anion exchangers. It consists of both Cation and Anion resins mixed together and filled
up. Hence the DM storage water is flowing through the mixed bed resins the traces of all
Cation and Anions are totally absorbed and removed.
The process of regeneration is similar to the regeneration process of Cation and anion
exchangers. After back washing the Cation gets settled at the bottom and the anion
resin at the top of the Cation bed. For regeneration the acid is introduced at the middle
and is taken out at the bottom. For anion regeneration the alkali is introduced at the top
and drained from the middle.
Conductivity meter:
The purpose of the conductivity meter is for continuously controlling the Demineralized
water effluent and signaling the exchange process exhaustion and consequent necessity
to regenerate the exhausted train.
Due to the extremely low salinity content of Demineralized water it would be impractical
to measure it gravimetrically. For this reason the more accurate and immediate electrical
conductivity measure of the Demineralized water is used, by taking advantage of the
capability of ions to conduct electric current in an aqueous solution. The higher the
salinity, the number of ions present the higher will be the electrical conductivity. Under
present circumstances 1 ppm of residual salinity corresponds to an electrical conductivity
of 5 micro-Siemens (at 20`C), thus giving a measure of operational leakage from the
Demineralized trains (normally ranging around 10 micro-Siemens or 2 ppm residual
salinity consisting of NaOH traces). When a stage of the Demineralized train is exhausted
the effluent salinity will rapidly increase and be signaled by a corresponding increase in
conductivity. As a general rule, under normally experienced conditions, a sharp increase
in the effluent conductivity is also matched by an increase (a marked increase) in the
silica content of the effluent. For this reason and to avoid over exhaustion of the resins it
is strongly recommended to regenerate the train as soon as a sharp increase in
conductivity is experienced (conductivity higher than 3 to 5 micro-Siemens). Slight
fluctuations in the recorded conductivity of effluent might be experienced without any
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special significance on the train operation, being due to slight fluctuations in filtered
water quality or rate of changes through the train.
Membrane Desalination Process (Reverse osmosis):
Reverse osmosis is a pressure
driven membrane process capable
of
removing
small
particles,
dissolved in salts and low molecular
weight organics from a feed water
stream. If two aqueous solutions
containing differential salt contents
are kept separated by a semipermeable membrane, the system
develops an inherent tendency for
water molecules (not the salt) to
permeate across the membrane
layer
to
dilute
the
more
concentrated solution.
This process is called osmosis. The driving force per unit membrane cross-section,
dependent on the concentration difference, is the osmotic pressure.
However, this natural process can be reversed if some external pressure higher than the
systems osmotic pressure is applied on the concentrated solution side whereupon water
will pass from the more concentrated solution, through the membrane boundary, to the
less concentrated solution. This is the basis of reverse osmosis.
If one compartment contains pure water
and the other salt or mineral-rich water,
the process of reverse flow will produce
pure water, since the membrane is not
permeable to salt.
The RO process cannot go on indefinitely.
The
salt
solution
would
require
increasingly higher pressure to force
water through the membrane; ultimately
the membrane could become clogged by
precipitated salts and other impurities. In
actual practice, RO devices employ crossflow filtration as shown in the figure here
This method uses a pressurized feed stream which flows parallel to the membrane
surface. Only a portion of this feed stream passes through the membrane as permeate
and the remainder of the stream known as the reject or concentrate provides a
continuous sweep of rejected ions and particles from the membrane surface.
Thermal Desalination Process:
It is based on using heat to vaporize a portion of the fluid (brackish water or sea water)
treated. The vapour is subsequently condensed as pure water. Basically, there are three
commercially available technologies by which thermal desalination can be accomplished:
Multiple effect distillation
Multistage flash evaporation
Vapour compression
The thermodynamic principles of operation for the processes are same; the processes
vary in method and operating conditions used to accomplish the desalination.
Zeolite Softening Processes
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This process, also known as zeolite softening, passes water through a filter containing
resin granules. In the filter, known as a softener, calcium and magnesium in the water
are exchanged for sodium from the resin granules. The calcium and magnesium in the
hard water are replaced by sodium ions
This method of water softening is been used extensively
for feed water treatment for smaller pressure boiler. It is
based on the ability of the ion-exchange resin Zeolite to
exchange one ion from the water being treated with
another ion in the resin. Zeolite resin exchanges sodium
ions for ions causing hardness in the water. Such ions are
the ions of calcium and magnesium present in the water
that flows through the Zeolite resin bed. The water
treated ends up with more sodium ions than before.
The ion-exchange softening process does not alter the
water's pH or alkalinity. In fact it actually induces an
increase in dissolved solids in the water. For each mg/l of
calcium removed and replaced by sodium, the total
dissolved solids increases by 0.15 mg/l. For each mg/l of
magnesium removed and replaced by sodium, the total
dissolved solids will increase by 0.88 mg/l.
Therefore by Zeolite Softening Processes, water doesnt become De-mineralized but only
becomes soft.
Chemical conditioning of Boiler water:
Demineralization of water renders raw water fit for use as make up and feed to a boiler.
Just feeding a boiler with Demineralised water, which is free of all impurities, alone, will
not suffice in reality due to the following reasons.
a) When the steam is continuously being generated and released for process, the
water inside the drum gets more and more concentrated, even with the very little
and negligible level of impurity in feed water.
b) Further the pH of Demineralized water normally remains to be close to neutral and
will induce low pH corrosion of tube and pipe materials.
c) Demineralized water when under storage absorbs atmospheric air and the level of
dissolved Oxygen in water increases. Presence of Oxygen in feed water again
renders it corrosive.
Hence it is essential and pertinent to further chemically treat the demineralised water,
which is taken as make up feed to boiler. Chemical treatment is done at various stages
for feed and boiled water, steam and return condensate, in order to ensure adequate
protection is established over the entire system, to help prevention of direct attack on
parent metal by the corrosive elements present in water / steam cycle.
We will learn about boiler water internal treatment process and its needs and effects in
detail in the following.
Chemical Treatment of Water in Steam Generating Systems:
The inhibition of corrosion in steam generators and auxiliary equipment during operation
is essential, for preventing damage to tube material and innumerous hazards caused,
generally resulting in equipment damage. Due to such damages, repairs and
maintenance expenditure increases demanding costly replacement of spare parts, in
addition to unwanted downtime, with corresponding loss of production. The iron and
copper corrosion products, from pre-boiler system, are often carried away into the boiler
and cause harmful scale deposits, contributing to caustic or hydrogen attack, as dictated
by conditions within the system.
Oxygen pitting - causes and remedy:
62

The presence of dissolved oxygen in boiler system water causes the cathode of any
corrosion cell to depolarize, thereby sustaining the corrosion process. The most familiar
form of oxygen attack in boilers and steam and condensate systems is pitting.
The presence of oxygen is also a necessary component of other corrosion mechanisms;
however, its role is less obvious. Dissolved oxygen is essential to ammonia corrosion of
copper alloy condenser tubes and contributes to chloride-induced stress corrosion
cracking of austenitic stainless steels in steam generators. It is, therefore, essential that
the dissolved oxygen concentration be kept at the lowest feasible and economically
justifiable level throughout all steam generating systems regardless of type, size or
pressure. This requirement grows more critical as the operating pressure increases and
as systems become larger, because the cost and danger of equipment failure increase
proportionately.
In larger and more complex systems, the major portion of dissolved oxygen can be
removed mechanically by such devices as deaerating feedwater heaters, condensers or
hot process softeners. It is important to note that mechanical deaeration must be
applied not only to the makeup water stream but also to any return condensate,
especially if the condensate return system operates under a vacuum, or if the
condensate receivers are vented to the atmosphere.
Under optimum operating conditions, it is often impossible for mechanical deaerators to
reduce the dissolved oxygen level below 0.005 cc/l or 0.007 ppm. Any deterioration in
Dearetor performance will result in increase of dissolved oxygen in feed water. The usual
practice is to resort to addition of chemical reducing agents to scavenge any residual
oxygen present in water.
Oxygen scavengers:
Feed water treatment with Sodium Sulfite (Na2SO3):
Sodium sulfite has long been used as an oxygen scavenger in boiler feed water
treatment. It reacts readily with oxygen, particularly at elevated pH and temperature, to
form sodium sulfate by the following reaction:
2 Na2SO3 + O2 2 Na2SO3
When any oxygen scavenger is used, it is essential to ensure total chemical deaeration
before the feedwater reaches the boiler. Especially it is essential to ensure this aspect,
while using sulfite, since oxygen remaining in the feedwater when it reaches the boiler
will flash into the steam phase, whereas the sulfite will remain in the water phase since
it is nonvolatile.
It is advisable to dose sodium sulfite to the condensate water or at the feed water
storage tank to ensure complete chemical deaeration in the preboiler section, so that it is
possible to allow sufficient reaction time for deaeration.
The reaction rate of sodium sulfite with oxygen is proportional to the concentration of
both sulfite and oxygen and to the temperature and pH of the feedwater. To ensure
complete oxygen removal when one of these factors is unfavourable, or when the
retention time allowed for the reason is short, a catalyst is often added to the sodium
sulfite to increase its reaction rate. Cobalt salts are the most commonly used materials
to catalyze the reaction.
Feed water treatment with Hydrazine (N2H4):
The widely used chemical oxygen scavengers in high pressure boiler operations is
hydrazine (N2H4). The advent of an organically catalyzed hydrazine suitable for use in
boilers made the full benefits of hydrazine available to low and medium pressure
applications and more extensive in high pressure systems.
The reaction of hydrazine with oxygen is as follows:
N2H4 + O2
>
2H2O + N2
It is important to note that the products of the hydrazine reaction are inert and volatile.
They will, therefore, not add any dissolved solids in the boiler water.
Hydrazine will also react with:
63

Ferric oxide
N2H4 + 6Fe2O3
> 4Fe3O4 + N2 + 2H2O
and Cupric oxide:

N2H4 + 4CuO
>
2Cu2O + N2 + 2H2O
Magnetite, Fe3O4, and cuprous oxide, Cu2O, are the passivated oxide states of iron and
copper. Hydrazine, therefore, renders iron and copper surfaces less susceptible to
corrosion by reducing them to a passive state. The reduction reactions take place on
metal surfaces in the pre-boiler, the boiler and the after-boiler, as well as on suspended
ferric oxide or cupric oxide. Hydrazine is fed in amounts required to react with dissolved
oxygen, ferric ions, and cupric ions, plus a small excess.
Initially the use of hydrazine was most extensive in high pressure boilers in which sulfite
would cause problems (as previously discussed). Hydrazines relatively sluggish reaction
with oxygen prevented its use in low pressure boilers. In high pressure systems, the
temperature of the boiler feedwater is usually sufficient to permit the effective use of
hydrazine. An organic catalyst was then developed which increased the reaction rate of
hydrazine with oxygen, permitting its effective use in boilers utilizing lower temperature
feed water. The increased reaction rate with catalyzed hydrazine brought the added
benefit of metal passivation and low temperature condensate protection to both high and
low pressure systems, even when a catalyst was not necessary for effective feedwater
oxygen scavenging. The basic reactions of catalyzed or uncatalyzed hydrazine are
identical except that in the case of the catalyzed version, reactions occur 10-100 times
faster.
Carryover of Boiler Water Priming and Foaming in boiler:
Mechanical entrainment is primarily a function of the design of the steam separators and
method of operation of the boiler. It can be aggravated chemically by conditions, which
produce foaming and thereby substantially increase the amount of droplets formed and
their entrance into steam separating equipment. The entrainment process may be
divided into two categories. One is being priming and the other foaming.
Priming:
Priming usually results from a sudden reduction in boiler pressure caused by a rapid
increase in the boiler steam load. This causes steam bubbles to form throughout the
mass of water in the boiler. Increased water volume raises the level in the drum,
flooding separators or dry pipe. Priming may also result form an excessively high water
level following a rapid load reduction caused by control failure.
Foaming:
Foaming is the buildup of bubbles on the water surface in the steam drum. This reduces
the steam release space and, by various mechanisms, causes mechanical entrainment.
Mechanical entrainment is usually controlled through proper design and subsequent
efficient operation, supplemented by the use of antifoam agents when foaming becomes
a problem.
Phosphate dosing and Corrosion in water tubes:
Water can enter the most nonporous of deposits on internal surface of the water wall
tubes. The water entrapped inside the deposit layer gets maximum heat absorption and
starts boiling. The ability of the main bulk of liquid to rinse the area at which the steam
bubbles form is, therefore, impaired, resulting in further concentration of solids. If the
boiler water composition is such that it becomes either strongly acidic or strongly basic
as it concentrates, under-deposit corrosion will usually occur.
While resorting the traditional high phosphate levels of 20 to 40 ppm, to make the
situation worse, simultaneously condenser tube leak also occurs, basic magnesium
phosphate deposits take place, rather than the desirable and less adherent basic
magnesium silicate (serpentine) or magnesium hydroxide (brucite). Hence in modern
64

high pressure boilers in order to prevent this type of magnesium deposition, the
concentration level of phosphate is reduced to 2 to 4 ppm of orthophosphate and the
hydrate alkalinity to 15 to 50 ppm as CaCO3. As operating pressure increase, waterwall
tubes exposed to high density of heat flux. It has been observed that although deposits
are controlled, failures do occur at times by metal losses characterized by large pits and
grooves develop.
Coordinated Phosphate-pH Control
This system, which is called coordinated phosphate-pH control, depends on the feed of
mixtures of orthophosphate or a mixture of caustic and disodium phosphate to control
pH in an otherwise un-buffered water. Monosodium, disodium, and trisodium phosphates
can accomplish this purpose as a result of their ability to hydrolyze to H2PO4 -, HPO4-2
and PO4-3 and to establish an equilibrium among these forms, in conjunction with OHconcentration or, by inference, the pH.
In water containing a low concentration of dissolved solids other than sodium phosphate,
the equilibrium between various forms of phosphate ion can be utilized to control the
acidity or alkalinity of the whole system. The ratio of one phosphate to the other can be
controlled to produce any desired sodium to phosphate (Na/PO4) ratio. If all of the
phosphate is present in the trisodium form, the Na/PO4 ratio is obviously 3.0. At or just
below this level there will be no free hydroxide present. The total free sodium hydroxide
or free caustic defines the amount of sodium hydroxide in solution in excess of that
derived from the hydrolysis of trisodium phosphate according to the following equation:
Na3PO4 + H2O Na2HPO4 + NaOH
The pH range for coordinated phosphate control should be 10.0 to 10.6. This
corresponds to an orthophosphate residual in the range of 15 to 50 ppm. The molar ratio
of sodium phosphate in the boiler water should be less than 3.0:1. Today, coordinated
phosphate control programs maintain a 2.8:1 Na/PO4 ratio. The phosphate residual is
generally controlled between 5 and 10 ppm as PO4 and the pH between 9.6 and 9.9. The
upper limit on operating pressure for this program is regarded as 100 kg/sq.cm
Volatile treatment
A review of high pressure boiler water treatment would not be complete without looking
at the alternative to phosphate programs. This program uses all-volatile treatment
chemicals and is commonly referred to as AVT or zero solids treatment. Sodium is
eliminated from the feedwater by evaporation and/or demineralization of the makeup
water and full flow, mixed bed demineralization of return condensate. No chemicals
containing sodium are added for internal treatment. The chemicals used are all volatile
materials are ammonia and/or morpholine or cyclohexylamine for pH control, and
hydrazine, catalyzed hydrazine or a volatile hydrazine substitute as an oxygen scavenger
and corrosion inhibitor. The control limits for an AVT program are total solids less than 2
ppm and a pH range of 8.5 to 9.0. Such treatment is limited to very high pressure
boilers, usually in steam-electric generating systems. It is the only treatment system
possible for once-through or monotube boilers, and most manufacturers of PWR-type
nuclear reactors favor its use in the secondary steam generating loop to overcome
unique crevice corrosion problems. It is occasionally employed in drum-type boilers
operating at 200 kg/sq.cm and above but provides less safety and corrosion resistance
against a temporary disturbance, particularly that of a condenser leak, than does the
phosphate-pH treatment system. In actual operation, most systems using volatile
chemistry provide a phosphate feeding facility for emergency use during a period when
feedwater is contaminated with dissolved salts.
As pressures increase, film boiling and other causes of local overheating are most
prevalent. This has led to the phenomenon known as caustic corrosion. Over
concentration of sodium hydroxide destroys the protective magnetic iron oxide film
(magnetite-Fe3O4), and the base metal is then attacked by the concentrated sodium
hydroxide as shown in the following two equations:
4NaOH + Fe3O4 Na2FeO2 + 2NaFeO2 + 2H2O
2 NaOH + Fe0 Na2FeO2 + 2H0
65

Caustic corrosion manifests itself as gouging and is fairly easy to identify. The tube does
not lose ductility and, unless arrested, the gouging proceeds until thinning eventually
causes tube failure.
It is generally accepted that caustic concentration in excess of 50,000 ppm or 5% is
necessary for the above reactions to occur. While there is never caustic present to these
levels in the bulk boiler water when using precision control, the concentrating
mechanism at the tube surfaces that can occur above 900 psig limits its use to lower
pressures.
Recommended Quality Parameters of Treated Water at Different Stages of
Treatment:
Clarified and filtered water (inflow to D.M. Plant):
We have seen in section 1.6 above what is meant by process of clarification and filtering.
The input to Demineralization plant must be clarified and filtered. The water inflow to
D.M. plant should be clear, colorless and odorless. It should be free from organic
matters, free from chlorine and other oxidizing agents. Presence of oxidizing agents,
organic matters etc. will affect the resin exchanging capacity and lead to total collapse of
the resin by way of decrosslinking. It should be free from iron, which leads to resin
surface contamination. pH control is equally important for maintaining raw water quality.
A preferable range would be 7 to 9.0.
Strongly acidic Cation effluent:
The quality of effluent water of strongly acidic cation exchanger will have the following
property:
PH at 25 C
Free mineral acidity ppm as CaCO3 (FMA)
[ HCl + H2SO4 + HNO3 + H3PO4 ] = [ Cl + SO4 +
NO3 + PO4 ]
2.8 to 3.5
Should be equal to the total equivalent
mineral acidity (EMA)
Hardness (Ca + Mg ) ppm as CaCO3
NIL
Sodium ppm as Na+
< 0.005
Degasifier effluent:
Residual free CO2 ppm
< 5.0
Strongly basic anion effluent:

The quality of effluent water of strong base anion exchanger will have the following
property:
pH at 25 C
7.5 to 9.0
Hardness (Ca + Mg) ppm as Ca CO3
NIL
Total silica SIO2 ppm
Less than 0.05
Electrical conductivity MICROMHOS/Cm at 25 C
< 2.0 preferably < 1.0
Chloride ( ppm as Cl )
NIL
Organic matter ( mg of KMn O4/Litre )
Practically free
66

Mixed bed effluent:
The quality of effluent water of mixed bed exchanger will have the following property:
pH at 25 C
6.8 to 7.2
PH less than 6.8 is an indication of leakage of
acidic sulphate and chloride salts and organic
acids. D.M. plant performance needs checking up.
Electrical conductivity micromhos/cm

at 25 C through closed cell provision
without any access to the atmosphere
< 0.2 micro seimensper sq.cm
Total hardness ( Ca + Mg ) ppm

CaCO3
NIL
Total silica ; ( SiO2 ppm :)
< 0.02 (< 0.01 is preferable )
Chloride ( ppm as NaCl )
NIL
( By selective ion electrode )

Sodium ( ppm as Na )
Organic matter mg of KmnO4/Litre
< 0.003
Should be practically free :
There may be slight consumption of permanganate. It
should be < 0.5 at any stage. < 0.2 is preferable. Blank
comparison is essential. For blank test use reagent
grade water.
General appearance
Clear, free from odour, colour and haziness. No

glittering to tyndal effect.
Condensate and Return condensate:

The quality of condensate depends upon the quality and the quantitative addition of
make up water. It is, hence, imperative to control CBD in order to limit make up
consumption. If auxiliary steam for various purposes is consumed, this will boost the
make up consumption. Under such circumstances, quality of make up should be closely
monitored to achieve the recommended values, so that, the quality of extracted
condensate is maintained. These recommendations are relevant for samples collected at
the condensate extraction pump delivery, prior to hydrazine (L.P.) dosing point.
Quality of extracted condensate water:
pH at 25 C
8.5 to 8.8
Electrical conductivity Micro mhos/Cm at 25 C
< 0.3
(with correction for ammonia and hydrazine
through strong cation column alone would
ensure the desired purity.)
Dissolved oxygen ( O2 ppm )
< 0.02
Dissolved carbon dioxide ( CO2 ppm )
NIL
Total iron ( Fe ppm )
< 0.01
Total copper ( Cu ppm )
< 0.003
Total silica : (SiO ppm )
< 0.01
Total hardness ( Ca + Mg ) ppm as CaCO3
NIL
Sodium + potassium ppm
< 0.01
Free ammonia : ppm
< 1.0 ( < 0.5 is preferable )
In order to get a reliable Conductivity and pH measurement the sample is to be cooled to

25 C with continuous flow of sample flowing with a closed cell provision having no
contact with atmosphere. The sample has to be passed through a strong acidic cation
column to avoid the influence of dissolved Ammonia and Hydrazine.
In case carbon dioxide is present in condensate water, the conductivity measured even
after passing through cation column will be indicated high, which will be proportional to
67

the concentration of carbon dioxide in the sample. Sample should flow at a regular and
constant rate and should be clear and colourless.
Drum sample quality is mainly dependent on the quality of the condensate extraction
and make up water. Feed flow requirement is decided by leakages and is dependent on
the drum operating pressure too.
Quality of feed water to boiler
Quality requirement for feed water is very much dependent on drum operating pressure.
Hence recommended feed water quality is always expressed for a particular range of
boiler operating pressure.
Drum operating
60
80
100
120
130 &
above
8.5~9.0
8.5 ~ 9.0
8.7 ~ 9.0
8.8 ~ 9.2
8.8~ 9.2
< 0.5
< 0.5
< 0.4
< 0.3
< 0.2
Economizer inlet
< 0.01
< 0.01
< 0.005
< 0.005
< 0.005
Total iron ( Fe ppm )
< 0.03
< 0.01
< 0.01
< 0.01
< 0.01
< 0.005
< 0.005
< 0.003
< 0.003
< 0.003
Total iron copper & nickel ppm
< 0.03
< 0.02
< 0.02
< 0.02
< 0.01
Total silica ( SiO2 ppm )
< 0.02
< 0.02
< 0.02
< 0.02
< 0.01
Nil
Nil
Nil
Nil
Nil
Pressure Kg/Cm2
pH at 25 C
Electrical conductivity at 25 C in
micro mhos/cm
Total copper ( Cu ppm )
Carbonic acid (CO2 ppm )

Organic matter mg KmnO4/Litre
Less than 0.1 ppm is considered tolerable
Oil ppm
Hydrazine N2H4 ppm )
Nil
Nil
Nil
< 0.1
< 0.05
< 0.05
Nil
Nil
< 0.02 ~ 0.05
< 0.02
Boiler water:
General requirements: The sample collected through CBD line should flow continuously
at a steady rate through a cooler. Temperature of the well condensed sample should not
be more than 25 C. There should be no appearance of red water when the flow is
disturbed. Sample collection with partial choking of line can lead to misleading results.
Lines may get choked with ferric and magnetic oxides. These oxides behave like weak
ion exchange resins and render the samples representation poor.
Boiler drum pressure kg/cm2
60
80
100
120
130
above
Electrical conductivity micro

mhos/cm at 25 C
< 300
< 200
< 100
< 50
< 50
Total solids ( ppm )
< 125
< 75
< 50
< 20
< 15
pH at 25 C
Total silica
10.0
10.5
( SiO2 ppm )
<5
9.8
10.2
<3
9.8
10.2
< 1.8
9.4
9.7
< 1.0
&
9.4 ~ 9.7
< 0.5
< 0.3 above 130Kg/Cm2

Phosphate (PO4
ppm )
7.0
11.0
Chloride
ppm )
< 5.0
(NaCl
5.0 ~
10.0
5.0
10.0
< 5.0
< 3.0
Free Hydroxide
3.0 ~ 6.0
3.0 ~ 6.0
< 3.0
< 2.0
To keep practically free
( NaOH ppm )
Phenolpthalene
alkalinity (CaCO3 ppm )
< 25
< 15
< 10
<5
<3
68

Conductivity:
Conductivity should be measured at 25 C at continuously flowing local point.
pH :
It is necessary to maintain pH/PO4 in accordance with coordinate control technique. Na
to PO4 ratio should be 3:1. For drum pressure rating of 130 Kg/Cm2 and above
congruent control is preferable. Here Na to PO4 ratio is kept at 2.6:1. Ideal range is
2.6/2.8 to 1; a combination of trisodium phosphates and disodium phosphates or sodium
hexameta phosphate and sodium hydroxide is used to pH/PO4 relation.
Chloride:
Presence of chloride is not desirable. Chloride ion impairs magnetite layers growth and
coherence. It retards healing mechanism. Even neutral or alkaline chloride may produce
acid. It is desirable to shut the unit if chloride ingress is from cooling water leakage,
D.M. plant leakage or from impure chemicals. In case of chloride contamination,
adequate pH and b/d control becomes necessary till normalcy is restored.
Free Hydroxide:
Free hydroxide should be maintained as low as possible, made practically free by
adopting coordinate/congruent technique. Na to PO4 ratio at 2.8 to 1, under normal
operating condition without any sulphate/chloride contamination, is ideal.
Saturated and Superheated Steam:
The objective is to obtain steam of very high purity, without any contamination from
dissolved and entrained solids and acidic gasses, in order to prevent fouling of super
heaters and turbine blades. Besides, the steam generated should be non corrosive to
ferrous and copper alloys and conducive to the preservation of protective Fe/cu passive
oxide layers.
Broad guide lines :
Solids ppm in steam
Turbine blade
deposition
Super heater
deposition
< 0.01
No
No
0.01 to 0.1
Possible
No
0.1 to 1.0
Yes
Possible
> 1.0
Yes
Yes
Steam sample should be collected through a well designed sampling device and cooler,
so that the sample collected is well condensed to a temperature of 25 C without
suffering solid separation or concentration.
pH at 25 C
8.9 to 9.2
The range is prescribed just to provide a safe guide line. It cannot be provided with
certainty for want of reliable and established data. However, to a great extent, pH
corresponding to a quantity of ammonia present in the steam, which when condensed
shall not exceed an average value of 0.5 ppm in the return condensate and at any time a
maximum value of 1.0 ppm can be relied upon. In the absence of carbon dioxide the
recommendation made is reliable and workable.
Electrical conductivity
< 0.3 and < 0.2 is ideal
Micro mhos/cm at 25 C
Conductivity is measured at 25 C at local continuous flow sampling point at the down
stream of a strong cation exchanger. Sample at a constant flow rate is passed through a
closed cell having no access to atmosphere. This in valid for CO2 free sample only. If CO2
is present, correction to the effect may give a value which may not be very reliable and
accurate.
69

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Steam Boiler - Training Workshop for Operators & Technicians