BOILER WATER TREATMENT AND TEST

By C/E Md. Azizur Rahaman

 Corrosion
• Most metals used has been processed
from there natural state and corrosion
of metals may be considered as the
returning of metal to its original form
of metal oxide.
• It is the gradual destruction of
materials (usually metals) by chemical
and/or electrochemical reaction with
their environment.
Corrosion
• Both the type of metal and the environmental
conditions, particularly gasses that are in contact
with the metal, determine the form and rate of
deterioration.
• The process of corrosion converts the reactive metal
surface into a more stable form, namely its oxide,
hydroxide, or sulfide.
Corrosion
Do All Metals Corrode?
All metals can corrode. Some, like pure iron, corrode quickly.
Stainless steel, however, which combines iron and other alloys, is
slower to corrode and is therefore used more frequently.
A small group of metals, called the Noble Metals, are much less
reactive than others. As a result, they corrode rarely. They are, in
fact, the only metals that can be found in nature in their pure
form. The Noble Metals, not surprisingly, are often very valuable.
They include rhodium, palladium, silver, platinum, and gold.
The main factors which affect corrosion
• More the reactivity of metal
• The impurities in material which increase the speed
of corrosion
• Presence of electrolytes in water also increases the
rate of corrosion
• A rise in temperature increases the rate of corrosion.
The main factors which affect corrosion
• Water:
• Oxygen:
• Temperature:
• Chemical Salts:
• Humidity:
• Pollutants: chlorides (in coastal areas), Acid gases,
such as carbon dioxide, promote corrosion.
How To Prevent Corrosion
You can prevent corrosion by selecting the right:
• Metal Type
• Protective Coating
• Environmental Measures
• Sacrificial Coatings
• Corrosion Inhibitors
• Design Modification
 The Chemical Reaction
Two distinct electrochemical reactions occur:
There is anodic dissolution or oxidation of iron
going into aqueous (water) solution:
2Fe → 2Fe2+  + 4e-
Cathodic reduction of oxygen that is dissolved
into water also occurs:
O2  + 2H2O + 4e- → 4OH-  
The iron ion and the hydroxide ion react to form
iron hydroxide: 
2Fe2+ + 4OH-  → 2Fe(OH)2
The iron oxide reacts with oxygen to yield red
rust, Fe2O3.H2O
Corrosion of metals in sea water
• If two dissimilar metals are placed next to each other in
presence of an electrolyte an electrical interaction will take
place.
• The electrical interaction mean that electrons and ions will
move between the two dissimilar metals and therefore
some chemical reactions will take place and will change
the structure of the material.
• This action is called galvanic action.
• This all happens more rapidly in presence of sea water!
 Galvanic Action
• Galvanic corrosion refers to corrosion damage
induced when two dissimilar materials are
coupled in a corrosive electrolyte. It occurs
when two (or more) dissimilar metals are
brought into electrical contact under water.
When a galvanic couple forms, one of the
metals in the couple becomes the anode and
corrodes faster than it would all by itself,
while the other becomes the cathode and
corrodes slower than it would alone.
Galvanic action/corrosion
In a galvanic action, the more
active metal (anode) corrodes at an
accelerated rate and the more
noble metal(the cathode) corrodes
at a slow rate. Factors such as
relative size of anode, types of
metal, and operating conditions
(temperature, humidity, salinity,
etc.) affect galvanic corrosion.
• Noble metals are metals
that are resistant to
corrosion and oxidation in
moist air. The short list of
chemically noble metals
comprises ruthenium,
rhodium, palladium, silver,
osmium, iridium,
platinum, and gold.
Methods of reducing galvanic effects:
• Choose materials close to each other in the series
• Make key component from a more noble metal
• Provide large area of the less noble metal
• Do not use graphite grease in presence of sea water
• Separate the dissimilar materials by an insulation.
Various types of corrosion
Graphitisation of cast iron:
corrosion in cast iron = graphitisation
Cast iron contains up to 3.5 % carbon,
which is mainly in the form of graphite
flakes(or spheroids) embedded in metal
matrix. In sea water the metal matrix
corrodes; graphite being the more noble
material; and graphite is exposed.
Various types of corrosion

Stress Corrosion:

Stress corrosion cracking (SCC) is the growth of crack formation

in a corrosive environment. It can lead to unexpected sudden
failure of normally ductile metals subjected to a tensile stress,
especially at elevated temperature.
Stress corrosion is most commonly found in brasses, but also
occurs in aluminum alloys and stainless steels.
 Various types of corrosion
Caustic Embrittlement:

Caustic embrittlement is the phenomenon in which the material

of a boiler becomes brittle due to the accumulation of caustic
substances.
This occurs as a result of local deposition of concentrated
hydroxide. Caustic embrittlement focuses on the stressed parts
of the boiler, including cracks, bends, rivets and joints.
Caustic embrittlement is also known as stress corrosion cracking.
 Caustic Embrittlement:

• As water evaporates in the boiler, the concentration of sodium carbonate

increases in the boiler. Sodium carbonate is used in softening of water by lime
soda process, due to this some sodium carbonate maybe left behind in the water.
As the concentration of sodium carbonate increases, it undergoes hydrolysis to
form sodium hydroxide.
• Na2CO3 + H2O → 2NaOH+ CO2
• The presence of sodium hydroxide makes the water alkaline. This alkaline water
enters minute cracks present in the inner walls of the boiler by capillary action.
Inside the cracks, the water evaporates and the amount of hydroxide keeps
increasing progressively. This sodium hydroxide attacks the surrounding material
and then dissolves the iron of the boiler as sodium ferrate. This causes
embrittlement of boiler parts like rivets, bends and joints, which are under stress.
 Caustic Embrittlement:
How to prevent Caustic embrittlement?
• Use suitable material
• Control stress level( avoid overloading, residual loads) A tube damaged by
• Avoid Alkalis caustic embrittlement.
• Control Temperature White caustic deposits
can be seen inside.
• by using sodium phosphate instead of sodium
carbonate as softening reagents.
• Adding tannin or lignin to boiler water blocks the
hair-line cracks and prevents infiltration of NaOH into
these areas.
Various types of corrosion
De-zincification:
Brass is an alloy of copper and zinc. In sea water, the zinc is
anodic to copper and it corrodes leaving a porous, spongy
mass of copper, hence de-zincification. This should not
occur to brasses in which arsenic has been added and
whose zinc content is less than 37%.
A similar attack, called de-aluminification, can occur to
aluminium bronzes. About 4 to 5% nickel added to the
bronze can avoid this problem.
Various types of corrosion
Fretting corrosion:
Fretting corrosion can occur where two surfaces in contract with each
other under go slight oscillatory motion, of a microscopic nature,
relative to one another.
Small relative motion causes removal of metal and metal oxide films.
The removed metal may combine with oxygen to form a metal oxide
powder that will, in the case of ferrous metal, be harder than the
metal itself, thus increasing the wear. Removed metal oxide films
would be repeatedly replaced, increasing the damage.
Fretting corrosion:
• Factors affecting the fretting corrosion:
• Damage increases with amplitude and frequency of
movement.
• Damage increasing with load carried by the surfaces
• Damage is reduced if oxygen level is low
• Damage decrease on the hardness of metal
• Damage increases in corrosive environment
• Damage increases with availability of moisture
Various types of corrosion
Pitting corrosion;

It is a localized form of corrosion by which cavities or "holes" are

produced in the material. Pitting is considered to be more dangerous
than uniform corrosion damage because it is more difficult to detect,
predict and design against. Corrosion products often cover the pits.
Pitting corrosion is caused when there is a relatively large cathodic
area and a small anodic area. Hence the intensity of attack at the
anode is high.
Pitting corrosion rate increases with higher temperature.
Causes of Boiler corrosion
•Oxygen present in boiler water
•Carbon Dioxide present in boiler water
•Presence of various salts in feed water
•Unbalanced pH of boiler water
•Exposure of boiler metal to dissolved gases present in boiler water
•Improper and unscheduled maintenance.
•Exposure of metal to the dissolved gases i.e oxygen and carbon dioxide
present in boiler feed water
•Caustic corrosion is caused by a concentration of caustic soda or sodium hydroxide
(NaOH).
•Thermal and mechanical stress in boiler
•Uncontrolled chemical treatment
PREVENTION OF CORROSION
• Proper water treatment
• Deareation of boiler feed water
• Proper pH maintenance
• Minimizing stresses through proper design & practice
• Control of deposits
• Control of oxygen & carbon dioxide present in boiler
feed water
Boiler Water Treatment
• Principal objects of boiler feed water Treatment:
• Prevention of scale formation by using distilled water or by
precipitating all scale forming salts into the form of a non-adherent
sludge.
• Prevention of corrosion in the boiler and in the feed system by
maintaining the boiler water in an alkaline condition and free from
dissolved gases.
• Control of sludge formation and prevention of carryover with the
steam.
• Prevention of entry of any foreign matter into the boiler such as oil,
waste, mill scale, iron oxides, copper particles, sands etc.
Boiler water treatment
• Filtration and ultra filtration
• De-areation or degasification
• Lime and soda treatment
• Caustic soda treatment(NaOH)
• Phosphate treatment
• Coagulants
• Condensate line treatment
• Prevention of caustic embrittlement
Lime and soda treatment

• Lime(calcium hydroxide, Ca(OH)2 and soda ash(sodium carbonate, Na2C03

are used to deal with calcium and magnesium compounds in boiler water.
• Calcium hydroxide, Lime, Ca(OH)2 reacts with temporary hardness salts and
magnesium compounds.
Ca(OH) 2+ Ca(HC03)2 --> 2 CaCO3 + 2 H2O
Sodium carbonate (soda ash, NaCO3 ) reacts with calsium compounds
originally in the water and those formed through using calcium hydroxide.
NaCO3 + CaSO4 → Na2SO4 + CaCO3
This combination of lime and soda gives zero hardness and alkaline feed
water.
Caustic soda treatment(NaOH)

• The most common alkalinity builder is sodium

hydroxide (NaOH, aka caustic soda).
• The foregoing treatments- lime soda, caustic soda –
have declined considerably in use. They have been
retained for completeness, interest and instruction as
they could prove useful in emergency condition.
• For the precipitation of scale forming salts and to
give alkalinity, phosphates are used.
Phosphate Treatment

• They are very effective scale inhibitors for low and high pressure boilers.
• Phosphate treatment precipitate calcium and magnesium hardness
from boiler feed water in the form of hydroxyapatite and serpentine.
These compounds form sludge, which, when properly conditioned with
polymers, is removed from the boiler via blowdown.
• Phosphates normally used as, sodium hexametaphosphate , sodium
metaphosphate, disodium phosphate and trisodium phosphate. The
metaphosphate are normally put into the feed system as they are
slower to react and therefore should not produce scale or sludge in the
feed system. Disodium and trisodium phosphate are usually pumped
directly into the boiler since they are quicker to react and could possibly
form sludge or scale in the feed system.
Coagulants

• The use of coagulants in the boiler is to condition the precipitates,

rendering them into the form of a sludge that is non adherent and
can easily blown out of the boiler.
• Coagulants used for boiler water are, polyelectrolytes(these are
synthetic organic polymers of high molecular weight).
• Coagulants form colloidal suspensions in the boiler water. Colloids
generally consist of sub-microscopic particles ( clusters of atoms or
molecules) which like electrical charge, and therefore repel each
other and prevent formation of large particles. They combine with
precipitates of opposite electrical charge to produce a floc or scum.
Coagulants
De-aeration
• Corrosion takes place in presence of oxygen by forming metal
oxides. Therefore if the air is removed from the feed water the
oxygen is also removed and hence de-aeration of feed water is
essential.
• De-aeration can be accomplished either mechanically or
chemically or a combination of both.
• The oxygen scavenging chemical used for de-aerating the water
usually sodium sulphite or hydrazine.
• Reaction of sodium sulphite and hydrazine
• 2 Na2SO3+ O2→2 Na2SO4
• N2H4+ O2→2 H2O + N2
Condensate line treatment

• Where the steam is wet , and also in the condensate

system, corrosion can occur due to the presence of carbon
dioxide carried over with steam.
• To ensure alkalinity in this section of system a volatile
alkaliser may be injected into the system line.
• These alkalisers are generally ammonia or cyclo-
hexylamine.
• If the ph value of the condensate is maintained at about 9
this should ensure no corrosion in low temperature steam
and condensate section of the plant.
Prevention of caustic embrittlement
• This can be prevented by using sodium phosphate instead
of sodium carbonate as softening reagents. Adding tannin
or lignin to boiler water blocks the hair-line cracks and
prevents infiltration of NaOH into these areas.
• Use suitable material
• Control stress level( avoid overloading, residual loads)
• Avoid Alkalis
• Control Temperature
 Boiler not in service/ Dry Storage
1. The unit should be cooled down and then completely drained.
2. Open all the manways and thoroughly wash the water side surfaces to remove
any sludge deposits. Mechanically clean residual particulate from the gas side
and water side
3. Dry the system thoroughly by using any heater unit.
4. Place some moisture absorbent, such as quick lime or silica gel.
5. After the entire system is dried the boiler system should be pressurized with
nitrogen to approximately 5 psi though the drum vent. Close the steam outlet,
drain valves, and feed water block valves.
6. Close all the openings to prevent water, steam or air leakage into the unit.
7. Isolate the boiler to prevent moisture from reaching the heating surface.
8. The lime/silica gel to be renewed atleast once in every two month.
 Boiler not in service /Wet Storage
• As the boiler is being shut down and as the pressure subsides, but before steaming stops, add
chemicals to the boiler to scavenge oxygen and to control pH, per the recommendations of the
Owner's water treatment consultant.
• When the boiler pressure gauge indicates about 10 psig completely flood the system with deaerated
treated water with the drum vent open. Close the drum vent after it begins to overflow. The steam
stop valve should already be closed.
• Close the feed water valves. Observe the steam drum pressure gauge and maintain pressure. If
pressure builds, it may be due to leaking feed water valves, which may not be properly seated. A
pressure loss (after the boiler is cool) indicates leakage, so check all fittings and valves for leakage.
• Frequent water samples should be taken and analyzed by the water treatment consultant. If the
analysis indicates a need for additional chemicals, the level in the boiler steam drum should be
lowered to normal level and chemicals added.
• Close all gas side access doors. Isolate the system to prevent cold air from reaching the heating surface
• During storage, steps should be taken to protect the exterior components from the possibility of rust
or corrosion.
Boiler water tests
Boiler water to be regularly tested and treatment of
boiler water to be as per test result.
Objectives of the Boiler Water Testing
• 1)To monitor the condition of the boiler water.
2)To control the chemical dosing of the boiler.
3)To maintain the boiler in healthy state,
4) To check any possible seawater contamination.
Boiler water tests
• Common tests includes;
1. Alkalinity test
2. Chloride test
3. Sulphate test
4. Phosphate test
5. Hardness test
6. Ph test
7. Dissolved oxygen test
8. Total dissolved solid test (TDS)
9. Hydrazine test
 PH Test
• The level of acidity or alkalinity is usually express
in terms of pH Value.
• This measure of hydrogen ions and hydroxyl ions,
when this are present in equal amounts the
solution is said to neutral. When there is an
excess of hydrogen ions it is acid, and when an
excess of hydroxyl ions it is alkaline.
• Keeping the water in slightly alkaline condition
reduces corrosion.
What is pH ?
• PH = Logarithm of the reciprocal of the
Hydrogen Ion in the solution
• It should be noted that as the
reciprocal is being use, the pH value
increases as the actual hydrogen ion
concentration decreases.
 Alkalinity test
Alkalinity is as the acid absorbing property of
water. Depending upon the pH of the water,
alkalinity can exist in water in three basic forms:
Carbonate(CO3)
Bicarbonate(HCO3)
Hydroxide(OH)
Alkalinity is measured by titrating a water
sample with a standard acid to a designated pH.
 Alkalinity test

• Alkalinity to Phenolphthalein(P-Alkalinity)
• Total Alkalinity(M-Alkalinity/T-Alkalinity)
• Caustic Alkalinity
P- Alkalinity

• Phenolphthalein is used as indicator.

• P alkalinity is determined by titrating
with sulfuric acid to a pH of 8.3
• P alkalinity endpoint is signaled by a
red to colorless color change.
• P alkalinity includes all the hydroxides
and half of the carbonate present.
M- Alkalinity
• Methyl orange is used as indicator
• M-Alkalinity is determined by titrating with
sulfuric acid to ph between 3.7 and 5.1
• The M-Alkalinity end point is signaled by a
green to purple color change.
• M-Alkalinity includes all the carbonate, by
carbonate and hydroxides. So is also the
measure of Total alkalinity.
 Caustic Alkalinity or OH Alkalinity

• Hydroxide OH alkalinity is determined by first treating

the sample with barium chloride to
precipitate/remove any carbonate that would
interfere with the test.
• The sample is next titrated with sulfuric acid to a pH
of 8.3.
• The OH alkalinity endpoint is signaled by ared to
colorless color change.
• OH-Alkalinity measures the hydroxides in the sample.
 Chloride test
• 1. Gives warning against any seawater
contamination of the Boiler Feed System.
2. Help to establish an effective blow down
control of the boiler.
 Chloride test
Procedures:
The range of chloride to be tested determines the size of water sample used. The higher
the chloride level, the smaller the size of water sample used – this saves tablets. E.g. for
Low Chloride Levels use 100 ml. water sample. For Higher Chloride Levels 50 ml water
samples.
1.Take the water sample in the stopper bottle provided.
2.Add one Chloride tablet and shake to disintegrate. Sample should turn yellow if chlorides
are present.
3.Repeat tablet addition, one at a time (giving time for the tablet to dissolve), until the
yellow color changes to permanent red/brown.
4.Count the number of tablets used and perform the following calculation:
For 100 ml Water Sample: Chloride ppm = (Number of tablets x 10) - 10 e.g 4 tablets = (4 x
10) – 10 = 30 ppm chloride
For 50 ml Water Sample: Chloride ppm = (Number of tablets x 20) - 20 e.g 4 tablets = (4 x
20) – 20 = 60 ppm chloride
For small steps of ppm chloride use a larger sample.
For larger steps of ppm chloride use a smaller sample.
5.Record the pH value obtained on the log sheet provided, against the date on which the
test was taken.
Phosphate ppm Test (PO4)
Purpose:
• To control the scale formation due to hardness
(presence of Phosphate in sample means no
hardness salts)
• It helps to maintain a phosphate reserve in the
boiler to counter any possible contamination of
the boiler water by corrosive and scale forming
salts. However, too much phosphate in the boiler
may also contribute to foaming and priming.
 Phosphate ppm Test (PO4)

• Procedures:

1.Take the comparator with the 10 ml cells provided.

2.Slide the phosphate disc into the comparator.
3.Filter the water sample into both cells up to the 10 ml mark.
4.Place one cell in the left hand compartment.
5.To the other cell add one Phosphate tablet, crush and mix until
completely dissolved.
6.After 10 minutes place this cell into the right hand compartment of
the comparator.
7.Hold the comparator towards a light.
8.Rotate the disc until a color match is obtained.
9.Record the result obtained on the log sheet provided, against the
date on which the test was taken.
Hydrazine/Amerzine Test

• To test for dissolved Oxygen content

• To know reserve hydrazine (N2H4 ) ppm
and to prevent corrosion and aeration.
• To minimize oxygen pitting and corrosion
in boiler, steam and condensate system.
• The hydrazine reserve in the boiler water
should be 0.1 and 1 ppm
 What is TDS ?
• Total Dissolved Solids (TDS) comprises of both Suspended and
Dissolved Solids. Substances that remain suspended in water and do
not dissolve in it are called suspended solids usually mineral or organic
in origin. Substances that are dissolved in water and cannot be seen by
naked eye are called dissolved solids. Dissolved solids generally include
sulfates and chlorides of sodium, magnesium, potassium and calcium
and these are mainly responsible for water hardness.
• Increase in the TDS concentration in boiler feed water leads to
increased scale formation or deposition on the tube surface, which act
as a resistance in transferring heat from flue gases to the water, which
further leads to overheating of the tubes.
TDS
 TDS test

• This is done by hydrometer or

electrical conductivity meter.
• The boiler water TDS may be measured either by:
• Taking a sample, and determining the TDS external to
the boiler, or by
• A sensor inside the boiler providing a signal to an
external monitor.
• boilers are normally operated with the TDS in the
range of 2 000 ppm for very small boilers, and up to 3
500 ppm for larger boilers,
Automatic TDS control
Recommended Boiler water quality
Thank you