Boiler

Boiler Water
Water Treatment
Treatment

- There is hardly an industry that does not make use of

boilers to generate steam

- The end use of steam varies from the driving force in

power generation to a multitude of applications and
processes as heating medium or reactant

- For boilers to operate efficiently, they require both a

high quality feed water and the maintenance of proper
water chemistry in the boiler
 Boiler Water
Problems

Corrosion Deposit Related

Related Problems
Problems

Corrosion Boiler
Scale
 Boiler
Boiler Scale
Scale
• One of the most common deposit problems is
boiler scale
• This happens when calcium, magnesium and
silica, common in most water supplies, react
with tube metal found in boilers to form a hard
scale on the interior of the boiler tubes,
reducing heat transfer and lowering the
boiler’s efficiency
Boiler
Boiler Scale
Scale
 Boiler
Boiler Scale
Scale Formation
Formation
• Scale is formed on boiler tube heating
surfaces by the depositing of impurities in
the feed water in the form of a more or less
hard adherent crust. Such deposits are due
to the fact the water loses its soluble power
at high temperatures or because the
concentrations become so high, due to
evaporation, that the impurities crystallize
and adhere to the boiler surfaces
Solubility
Solubility of
of Mineral
Mineral Salts
Salts in
in
Water
Water
 Effect
Effect of
of Boiler
Boiler Scale
Scale
• 1/8-inch (3mm) of scale can cause a
2.0-3.0% loss in fire-tube boilers and
water tube boilers.
• A second but more serious effect from
scale is the overheating of boiler tube
metal, causing eventual tube failure. In
modern boilers with high heat-transfer
rates, even extremely thin layers of
scale will cause a serious elevation in
the temperature of tube material
 Corrosion Related Problems
Corrosion is due to the acidity/or oxidizing
properties of the feed water
 Pitting Corrosion
Which consists of isolated spots of active corrosion
caused by Oxygen attack

 General Corrosion
Produced by an acid attack mainly due to the
presence of CO2 which dissolve in water forming
carbonic acid (H2CO3)
 Pitting Corrosion
• Dissolved oxygen interacts with boiler component
surfaces, forming “pits” on the metal surface.
• These pits may eventually grow large enough to
penetrate the metal forcing a boiler shutdown.
 Pitting
Pitting Corrosion
Corrosion
• Dissolved oxygen in boiler feedwater
intensifies the corrosion of boiler tubing, by
acting as a depolarizer agent, and accepting
free electrons liberated from the surface of the
boiler tubing, and is instrumental in
determining the intensity of waterside
corrosion of boiler tubing.
• Fe - 2e---->Fe2+
• O2 + 2H2O + 4e -------->4OH-
• Fe2+ + 2OH- --------> Fe(OH)2
 Pitting
Pitting Corrosion
Corrosion
• The presence of oxygen in condensate can be
caused by poorly operating deaerators, leakage
of air into vacuum condensers, and leakage of
cooling water.
• Oxygen in the boiler feed water becomes
extremely aggressive when heated.
• In addition to tube corrosion, further damage
may occur to steam and mud drums.
Pitting
Pitting Corrosion
Corrosion
 General Corrosion
• The most common cause of general
corrosion is the presence of carbon
dioxide (CO2) in the boiler feed water and
the condensate.
• Carbon dioxide form carbonic acid and
reduce the pH of the condensate and
acid attack while oxygen directly attack
metal.
 General Corrosion

• Carbon dioxide dissolved in water liberates

H+ ions that attacks the metal.

CO2+H2O <=====>H2CO3
H2CO3 <======> HCO-3 + H+
General
General Acidic
Acidic Corrosion
Corrosion
 Treatment Processes

• External treatment

• Internal treatment

• Condensate treatment
 Softening
Softening
HARDNESS

MAGNESIUM CALCIUM
HARDNESS HARDNESS
Caused by magnesium Caused by calcium ions
ions (Mg2+) (Ca2+)

TOTAL HARDNESS
It is the sum of the hardness caused by both
calcium and magnesium ion.
 Softening
Softening

Cations Causing Hardness Most Common Anions Causing

Hardness

Calcium, Ca2+ Bicarbonate, HCO3-

Magnesium, Mg2+ Sulphate, SO42-

Strontium, Sr2+ Chloride, Cl-

Iron, Fe2+ Nitrate, NO3-

Manganese, Mn2+ Silicate, Sio3-

 Softening
Softening
Presence of Calcium and
Magnesium Ions
(Ca2+, Mg2+)

Domestic Problem Industrial Problem

Cause a coating
to form inside
Food
water heater
processing

Difficulties in doing
the laundry and
dishwashing.

Shorten the life

of fabric
Boiler and steam
washed in hard
production.
water.
(problem of scale
forming)
 Softening
Softening

Calcium Hardness mg/L as CaCO 3 = 2.5 x calcium concentration

mg/L

Calcium Hardness mg/L as CaCO 3 = 4.12 x magnesium concentration

mg/L
 Chemical
Chemical Precipitation
Precipitation

SOLUBLE FORM
HARDNESS INSOLUBLE
FORM
HARDNESS

Chemical Reaction
 Softening
Softening
T h e e q u a tio n s b e lo w d e s c rib e th e re m o v a l o f c a rb o n a te h a rd n e s s .

C a (H C O 3 ) 2 + C a (O H ) 2  2 C a C O 3 + 2 H 2 O

M g (H C O 3 ) 2 + C a (O H ) 2  C a C O 3 + M g C O 3 + 2 H 2O

M g (H C O 3 ) 2 + C a (O H ) 2  C a C O 3 + M g (O H ) 2 + 2 H 2 O
Ion Exchange
(Softening)
Cations Anions

Calcium Bicarbonate
Magnesium Chloride
Sodium Sulfate
Iron Nitrate
Manganese Carbonate
Demineralisation
Demineralisation
In the demineralizer, water is treated in two
steps. First, it is passed through the cation ex-
change bed, where the cations (calcium,
magnesium and sodium) are exchanged for
hydrogen ions. The treated water is now free of
cations but is too acidic and cannot yet be used
in the boiler.
In the second step the water passes through the
anion exchange bed where the anions (sulfate,
chloride, carbonate and silica) are ex-changed
for hydroxide ions. The hydrogen and hydroxide
ions react to form water, now suitable for use in
the boiler.
Cation
Cation Exchange
Exchange
Anion
Anion Exchange
Exchange
Mixed
Mixed Bed
Bed Ion
Ion Exchange
Exchange (Polishing)
(Polishing)
Softener
Softener Regeneration
Regeneration
Cation
Cation &
& Anion
Anion exchangers
exchangers regeneration
regeneration
Cation
Cation &
& Anion
Anion exchangers
exchangers regeneration
regeneration

• Regeneration of cationic resins is

performed by means of 6% Sulphuric
Acid (H2SO4) and regeneration of anion
resins is performed by 3% Sodium
Hydroxide (NaOH) dosed by metering
pumps.
• The regeneration (dilution) water is
polished water.
 Deaerator/Degasifier
Deaerator/Degasifier

• The removal of dissolved gases from boiler

feed water is an essential process in a steam
system.
• Deaeration is based on two principles
The gas solubility in a solution decreases as the gas
partial pressure above the solution decreases.
The gas solubility decreases as the solution
temperature increases.
 Deaerator/Degasifier
Deaerator/Degasifier

• The following parameters are very

important to insure the correct operation of
the deaerator:
The deaerator operating pressure should be 2-4 psi
above atmospheric
Water temperature should be 8 degrees Fahrenheit
above the boiling point of water at the altitude of the
installation.
18-24 inch steam plume visible at the deaerator vent
 Internal
Internal Treatment
Treatment

• Oxygen Scavengers
 Hydrazine N2H4
 Hydrazine sulphate N2H4.H2S4

 Hydrazine hydrate N2H4.H2O

N2H4+O2----->N2+2H2O

 ٍٍSodium Sulfite NaSO3

2Na2SO3+02---->2Na2SO4
 COMMON BOILER FEEDWATER
CONTAMINANTS
IMPURITY RESULTING IN GOT RID OF BY COMMENTS

Soluble Gasses

Water smells like rotten eggs: Tastes bad, Found mainly in groundwater, and polluted
Hydrogen Sulphide (H2S) and is corrosive to most metals.
Aeration, Filtration, and Chlorination.
streams.

Corrosive, forms carbonic acid in Filming, neutralizing amines used to prevent

Carbon Dioxide (CO2) condensate.
Deaeration, neutralization with alkalis.
condensate line corrosion.

Deaeration & chemical treatment with Pitting of boiler tubes, and turbine blades,
Oxygen (O2) Corrosion and pitting of boiler tubes.
(Sodium Sulphite or Hydrazine) failure of steam lines, and fittings etc.
 Internal
Internal Treatment
Treatment
1-Sodium Phosphate

• It buffers the boiler water pH to minimize the

potential for boiler corrosion.
• It precipitates small amounts of calcium or
magnesium into a soft deposit which can then
accumulate in mud drums or steam drums
rather than as hard scale.
• It helps to promote the protective oxide film
on boiler metal surfaces
2-Phosphate and Polymers

• This type of program causes sludge to form and

therefore requires continuous blowdown.
Deposition problems are possible in the higher
heat transfer areas of the boiler. On the positive
side, phosphate-polymer programs can
essentially handle any feed water hardness and
be cost effective. This is particularly true of the
new synthetic polymers.
3-Chelates and Polymers

• Rather than precipitate with hardness

compounds, chelates and polymers
“solubilize” or combine with hardness
(calcium and magnesium and to some
extent iron) to form a stable chemical
compound. Sometimes they are used in
conjunction with phosphate. The
resulting compounds can be eliminated
by blow down.
 Blowdown Treatment
• Blowdown is a very important part of any
water treatment program. Its purpose is to
limit the concentration of impurities in the
boiler water.
• The right amount of blowdown is critical: too
much results in energy loss and excessive
chemical treatment cost; too little and
excessive concentrations of impurities build
up.
• It can range from 1% (based on feedwater
flow) to as much as 25%.
1-Bottom Blowdown

• By definition, bottom blowdown is

intermittent and designed to remove sludge
from the areas of the boiler where it settles.
The frequency of bottom blowdown is a
function of experience and plant operation.
Bottom blowdown can be accomplished
manually or electronically using automatic
blowdown controllers
2-Continuous Blowdown

• Frequently used in conjunction with manual

blowdown, continuous blowdown constantly removes
concentrated water from the boiler. By design, it is in
the area of highest boiler water concentration. This
point is determined by the design of the boiler and is
generally the area of greatest steam release.

• Continuous blowdown allows for excellent control

over boiler water solids. In addition, it can remove
significant levels of suspended solids. Another
advantage is that the continuous blowdown can be
passed through heat recovery equipment.
 Condensate Treatment
• Corrosion of condensers, steam traps
and condensate piping is common
• Neutralizing amines can only protect the
system from acid attack due to carbon
dioxide.
• Certain compounds form a very thin film
of organic material on metal surfaces,
which acts as a barrier to oxygen but has
little effect on the pH of the condensate.
There is minimal effect on heat transfer
because the film is thin
1.Neutralising Amines

• Simply stated, neutralizing amines hydrolyze in

water to generate the necessary hydroxide ions
required for neutralization of the carbon dioxide.
The normal approach to treating systems with
these amines is to feed sufficient quantity to
neutralize the carbon dioxide and then provide
small additional amounts to buffer the pH to 8.5 or
9.0. At this pH, continued preservation of the
magnetite film is also achieved. It is also implied
that corrosion will not exist at a pH>8.0-8.5.
1.Neutralising Amines

Neutralized Amines • A variety of

Morpholine amines are
available for
Diethylaminoethanol condensate
neutralization
Dimethylisopropanolamine
and pH elevation
• Frequently, a
Cyclohexylamine
blend of amines
Ammonia
may appear to be
optimum
2-Filming Amines.

• Filming amines function by forming a

protective barrier against both oxygen and
carbon dioxide attack. These amines form
films directly with the condensate line metal
and develop a barrier to prevent contact of
the corrosive condensate with the return
piping. By design, film formers have been
developed to function best at a pH of 5.5-
7.5.
3-Combination Amines.

• Combinations of filming and neutralizing amines

have been shown to be extremely effective,
particularly in complex systems. While the
combination amine is still functionally a filmer,
the neutralizing amine portions provide for
reduction in fouling potential and more uniform
coverage of the filmer.
• Filming amines and combination amines are
generally fed to steam headers. Dosages are based
on steam production.
 Carryover
Carryover Problem
Problem

• Carryover is generally considered to be any

contaminant that leaves a boiler steam drum
with the steam. It can be in solid, liquid or
vaporous form. With higher operating
pressures, higher superheat temperatures
and the need for pure steam in certain
processes, greater emphasis is placed on
controlling the factors that minimize
carryover.
 Carryover
Carryover

For the sake of clarity, certain definitions are

required:
1. Steam Purity -The amount of solid, liquid or
vaporous contamination in the steam. Steam purity
is normaily reported as total solids in parts per
billion (ppb).
2. Steam Quality -The amount of moisture in the
steam. It is the weight of dry steam in the mixture
of steam and water droplets. It is reported as a
percentage.
 Carryover
Carryover Effects
Effects

Some of the effects of carryover are:

1. Deposition in regulators and valving
2. Deposition in superheaters
3. Deposition in control valves and turbines
4. Process contamination
 Causes
Causes of
of Foaming
Foaming

Generally, the causes of foaming are linked to

the following:
1. High dissolved solids concentrations in the
boiler water
2. High suspended solids concentrations
3. High alkalinity concentrations
4. Oil Contamination
Standard Boiler Water Concentrations for
Minimizing Carryover
Boiler Water
Drum
Pressure Total Specific**
Resistivity
(psig) Silica* Alkalinity
(micromhos/cm)
(ppm SiO2) (ppm CaCO3)
0-300 150 700 7000
301-450 90 600 6000
451-600 40 500 5000
601-750 30 400 4000
751-900 20 300 3000
901-1000 8 200 2000
1001-1500 2 0 150
1501-2000 1 0 100