Boiler Water Treatment

The water cycle

What Causes Problems?

Scale forming salts.
Sludge.
Metals and metal oxides.
Acidic water.
Dissolved gasses.
Excessive alkalinity.
Oils.

The Impurities

Problems With Salts

Sea Water
Sodium Chloride

NaCl

24,600 p.p.m.

Magnesium Chloride

MgCl2

3,120 p.p.m.

Magnesium Sulphate

MgSO4

1,870 p.p.m.

Calcium Sulphate

CaSO4

1,250 p.p.m.

Calcium Bicarbonate

Ca(HCO3)2 320 p.p.m.

Silicate

SiO3

8 p.p.m.

Problems With Salts

Fresh water
Calcium Carbonate

CaCO3

200 p.p.m.

Calcium Sulphate

CaSO4

90 p.p.m.

Sodium Chloride

NaC1

50 p.p.m.

Sodium Nitrate

NaNO3

35 p.p.m.

Magnesium Sulphate

MgSO4

30 p.p.m.

Silicate

Si03

trace.

Hardness Salts
Salts react when the water in which they are
dissolved is heated and are defined as either: Temporary hardness salts.
Permanent hardness salts.

Hardness Salts
Temporary hardness salts :
typically calcium bicarbonate
These are alkaline salts and will
decompose when the water is
heated to about 100C and produce
carbon dioxide and scale (chalk).

Hardness Salts
Permanent hardness salts :
typically calcium sulphate

These are non-alkaline salts and will

remain dissolved at 100C but will
cause problems with scale and acidity
as the water is further heated.

Hardness Salts
Total hardness:Is the sum of the temporary and permanent
hardness salts and is an indication of the
total scale forming potential of the water.

Hardness Salts
Solubility rule
Salts whose solubility decreases with an
increase in temperature are those that form
scale.
Salts whose solubility increases with an
increase in temperature do not normally form
scale but will tend to form sludge if the
saturation point is reached:
example - sodium chloride (table salt).

Effect of Heating Seawater

Sodium Chloride Calcium Bicarbonate
Calcium Sulphate Magnesium Carbonate
Magnesium Sulphate.

No scale

< 80C

Carbonate scale

< 130C

Sodium Chloride
Magnesium Carbonate
Magnesium Sulphate

Calcium Sulphate scale

< 185C

Sodium Chloride

Magnesium Carbonate.
Magnesium Sulphate.
Scale & acid conditions

> 185C

Sodium Chloride Calcium Sulphate

Magnesium Carbonate
Magnesium Sulphate

Calcium bicarbonate - Chalk

Comes out of solution at about 100C to form soft chalk
scale and liberate Carbon dioxide gas:Ca(HCO3)2 >

CaCo3 +

CO2 +

H2O

Calcium bicarbonate > Chalk + Carbon dioxide + Water.

Carbon dioxide will combine with the water to produce
Carbonic acid.
Carbonic acid will then corrode the steel to produce Ferrous
Carbonate + Hydrogen gas.
The Ferrous carbonate will then combine with Oxygen and
Water to produce Ferrous hydroxide and more Carbon
dioxide.

Calcium bicarbonate - Chalk

Carbon
dioxide
Calcium
bicarbonate

Water

Hot water

Chalk scale

Ferrous
hydroxide

Carbonic
acid

Ferrous
carbonate

Ferrite
(steel)

Water

Hydrogen

Sodium Chloride - Table Salt

Sodium chloride has a very high solubility level, which
increases with temperature and it will not, therefore, come
out of solution to form scale.

Sodium chloride contamination will accumulate within the

boiler, increasing the density of the water and eventually
cause problems with circulation, foaming, priming and
carry-over.

Calcium Sulphate
A dangerous scale forming salt.
The solubility of calcium sulphate decreases as
the temperature increases and it will start to
deposit and form scale at a temperature of 138C
(3.5 bar saturated pressure)
The scale formed is hard and difficult to remove.
It has excellent insulation properties that can
cause localised overheating and eventual boiler
failure.

Magnesium Chloride
Remains soluble within boiler water and will not in itself
form scale.
But at a temperature of about 182C (or 10.5 bar saturated
pressure) it will start to react with the water to form
Hydrochloric acid and Magnesium hydroxide: MgCl2 + 2H2O > Mg(OH)2 + 2HCl
The Magnesium hydroxide can form scale.
The Hydrochloric acid will react with the ferrous metal of
the boiler and cause acid corrosion which will be self
sustaining.

Magnesium Sulphate
- Epsom Salt
Magnesium sulphate remains soluble within boiler water up
to a temperature of about 182C (or 10.5 bar saturated
pressure)
At this point, if the density is high enough, it will start to
deposit as scale.
It can also react with sodium chloride to form sodium
sulphate and magnesium chloride.

Silicate
Silicates can form a very hard thin glass-like insulating
scale within the boiler and can also carry-over with the
steam as silicic acid into superheaters and turbines.
Mainly a problem with high pressure boilers.
Silicate scale is extremely difficult to remove and
requires the use of specialists and very hazardous
chemicals.

The Effects of Scale

The Effects of Scale

No Scale

3mm Scale

1400C

1400C

530C
Boundary
layer

510C

220C
200C

180C

Furnace Tube wall Water side

Efficient heat transfer. No stress

180C

Furnace Tube wall

Water side

Inefficiency. Stressed steel. Failure

Result of Scale

Insulation Effects
(Aalborg Industries)

No
sediment

Insulation capacity [W/(m x K)]

2 mm
carbonate

0.5 mm
silica

0.5 mm oil
film

1.72

0.172

0.10

Heat transfer [kW/m2]

137

119

98.7

82.3

Surface Temp Steel @ interface C

184

320

467

590

Interface Temp @ water/sediment. C

184

181.9

179.9

178.2

Furnace Wall Temperature C

256

382

519

633

Transferred heat is reduced from 137 kW/m2 to 119 kW/m2, a

reduction of 14%.
The maximum temperature of the furnace wall is increased from
256C to 382C with 2mm of scale.

Insulation Effects
(Aalborg Industries)

No
sediment

Insulation capacity [W/(m x K)]

2 mm
carbonate

0.5 mm
silica

0.5 mm oil
film

1.72

0.172

0.10

Heat transfer [kW/m2]

137

119

98.7

82.3

Surface Temp Steel @ interface C

184

320

467

590

Interface Temp @ water/sediment. C

184

181.9

179.9

178.2

Furnace Wall Temperature C

256

382

519

633

Transferred heat is reduced from 137 kW/m2 to 98.7 kW/m2, a

reduction of 28%.
The maximum temperature of the furnace wall is increased from
256C to 519C with silica scale just 0.5 mm thick.

Iron
Iron may enter the boiler as a result of corrosion. Iron oxide
will be deposited and retard heat transfer and stop water
circulation within boiler tubes.
Iron oxide can appear as rust, the red oxide form, when it is
fully oxidised.
Usually, in a properly maintained boiler with limited
oxygen, iron oxide appears in the reduced or black powder
form as magnetite (Fe3O4) and can be considered normal.

Copper Plating
Copper is introduced into boilers by corrosion of copper
piping and copper alloys in the feed system.
Copper in the boiler plates out on the tubes, often under
existing scale and sludge deposits where it acts as a very
efficient insulator.
Copper depositing is a serious on-going problem in high
pressure boilers and requires them to be chemically cleaned
at regular intervals.

Heat transfer loss %

7
6
5
4
3
2
1
0.4

0.8

1.2

Scale thickness mm

1.6

Ionisation
Water (H2O) based solutions will tend to partially
dissociate into positively charged Hydrogen ions (H+) and
negatively charged Hydroxyl ions (OH-).
Acid solutions contain more Hydrogen ions (H+) than
Hydroxyl ions.
Alkaline solutions contain more Hydroxyl ions (OH-) than
Hydrogen ions.

pH
To obtain the pH, the number of H+ ions in a particular
solution is counted.
The numbers involved are large, so to simplify things the
negative log10 of the number (or count the number of
decimal places.) is taken. Therefore:Hydrochloric acid = 0.01 H+

= pH2

Pure water

= pH7

= 0.0000001 H+

Sodium hydroxide = 0.00000000000001 H+ = pH14

The pH Scale
Acid

Neutral

Alkaline

10

Any solution with a pH below 7 is acid.

Any solution with a pH above 7 is alkaline.

11

12

13

14

Problems With Acidity

Acid conditions in a boiler or feed system will cause
corrosion of the steel.
Acidity in feed water is primarily caused by absorption of
Carbon dioxide from the air, or from the formation of chalk
scale, producing Carbonic acid in the water.
If water containing Magnesium chloride is heated above
182C in the boiler then Hydrochloric acid will be formed
which is even more aggressive.

Acidic Corrosion
Water that becomes acidic (<pH6) will chemically attack
any ferritic materials (e.g. steel) and cause overall wastage.
The following shows the chemical reactions of Carbonic
acid and Hydrochloric acid with iron.
H2CO3 + Fe

> FeCO3 + H2

(Carbonic acid + Iron > Ferrous carbonate + Hydrogen)

2HCl + Fe

> FeCl2 + H2

(Hydrochloric acid + Iron > Ferrous chloride + Hydrogen)

If steel is left in contact with acid it will slowly dissolve
away.

Problems With Alkalinity

Alkaline conditions in a feed system or boiler will
neutralise acidity and reduce or eliminate corrosive attack.
Excess alkalinity can, however, cause a phenomenon
known as caustic cracking or gouging which can cause
boiler failure.

Excessive Alkalinity
Sodium hydroxide (caustic soda), used to eliminate acidity
in boiler water, can cause a phenomenon known as caustic
embrittlement.
High concentrations of sodium hydroxide and high residual
stress in the boiler material can combine to cause cracking
in the steel.
This phenomenon is mainly associated with residual stress
in older riveted boilers.
Modern welded boilers are stressed relieved but caustic
embrittlement can happen where leakage is allowed to
occur at boiler mountings, door joints etc.

Caustic Cracking
The concentration of sodium hydroxide required for caustic
cracking to occur is about 85,000 p.p.m. at 200 - 250C.
Normally such concentrations would never be found in a
boiler, but leakage at seams where water is flashed off to
steam, can lead to high concentrations of salts.
The stress corrosion cracks formed follow the grain or
crystal boundaries of the material and can result in failure.

Caustic Cracking

Leaking joint
Cracking

High concentration
of caustic alkalinity

Typical boiler mounting

(feed check, blow down valve etc)

Caustic Corrosion
Caustic corrosion or gouging, can occur in modern welded
boilers (group 4 and above).
Boiler water, carrying dissolved Sodium hydroxide, forms
caustic concentrations as high as 100,000 p.p.m. under any
scale or magnetite film on the tubes.
Caustic corrosion typically appears in the form of irregular
pits or gouges in the steel.

Caustic Corrosion

Problems With Oxygen

Water will naturally ionise into hydrogen ions (H+) and
hydroxyl ions (OH-).
The structure of steel (Fe) will lead to parts becoming
electro-positive (anodic) and parts becoming electronegative (cathodic.)

H+

Ionised H2O

Cathodic area

Fe

OH-

Anodic area

No Oxygen Present
Ionised H2O
H+

OHFe(OH)2

HHHHH
Electrons
Cathodic area

Fe+
Anodic area

H+ ions will be attracted to the cathodic area, claim an

electron from the iron and becoming hydrogen atoms.
OH- ions will be attacted to the anodic area, combine with
the positive ferrous ions and form ferrous hydroxide.

No Oxygen Present
Ionised H2O
H+

OHFe(OH)2

HHHHH
Electrons
Cathodic area

Fe+
Anodic area

If the pH is >6 and no oxygen is present, then the hydrogen

atoms will form a stable layer on the surface of the metal.
The ferrous hydroxide will remain insoluble and no further
corrosion will take place.

Oxygen Present
O2

Ionised H2O
H+

O2
OH-

Fe2O3
H 2O

H HH
Electrons
Cathodic area

Fe+
Anodic area

If oxygen is present in the water (and pH <10) then the ferrous

hydroxide will react with the oxygen to form ferric oxide
Fe2O3 (red rust) and a pit will start to form in the steel.
The oxygen will combine with the hydrogen atoms to form
water, the cathodic area will then be re-exposed and corrosion
will continue.

Pitting Corrosion

Pitting corrosion

General wastage

Rate of
corrosion

Medium oxygen

High oxygen

Zero oxygen

No corrosion

Low oxygen

7
pH

10

11

12

13

Oil Contamination
Oil of any type or quantity cannot be tolerated in any steam
raising plant.
Light oils will evaporate and pass over with the steam
and will cause problems by carbonising in superheaters
etc.
Heavy oils will mix with scales and suspended solids,
carbonise and form a very dangerous insulating barrier
on the heat transfer surfaces within the boiler.
Lubricating oils with detergent properties will form a
stable emulsion with the boiler water and eventually
cause the same problems.

Oil Contamination
If leakage is detected in the boiler then the whole feed
system will also be contaminated and this will include
pipework, hotwell, feed pumps etc.
Oil originates from fuel, lub oil or cargo heating systems
and indicates leakage in the heating coils.

Insulation Effects
(Aalborg Industries)

No
sediment

Insulation capacity [W/(m x K)]

2 mm
carbonate

0.5 mm
silica

0.5 mm oil
film

1.72

0.172

0.10

Heat transfer [kW/m2]

137

119

98.7

82.3

Surface Temp Steel @ interface C

184

320

467

590

Interface Temp @ water/sediment. C

184

181.9

179.9

178.2

Furnace Wall Temperature C

256

382

519

633

Transferred heat is reduced from 137 kW/m2 to just 82.3 kW/m2,

a reduction of 40%.
The maximum temperature of the furnace wall is increased from
256C to 633C with an oil film of just 0.5 mm.

Boiler & Feedwater Treatment

The principles of boiler & feed water treatment are:
Prevention of scale formation on the surfaces of the
boiler and feed system.
Prevention of corrosion in the boiler and feed system.
Prevention of foaming and water carry-over into the
steam system.
Control of sludge formation within the boiler.

Boiler & Feedwater Treatment

The first and primary means of achieving the requirements
is to ensure that only waters low in dissolved solids are
used as make up feed.
Ideally only pure de-mineralised water should be used and
this is mandatory for high-pressure water tube boilers of
group three and above.
A lesser quality of water may be tolerated for use in group
one fire tube boilers.
Under no circumstances, excepting in the direst of
emergencies, should raw seawater be used in boilers.

Treatment Chemicals
Sodium carbonate (Soda ash).
Calcium hydroxide (Lime).
Sodium hydroxide (Caustic soda).
Sodium phosphate (Calgon).
Hydrazine.
Amines.
Anti foams.
Sludge Conditioners.

Lime-Soda Treatment
The chemicals originally used for the treatment of low
pressure boilers.
Calcium hydroxide (lime) is used in conjunction with
sodium carbonate (soda ash).
How it works: Calcium hydroxide reacts with the scale forming salts to
produce non-adhering sludge.
Sodium carbonate is converted into Sodium hydroxide,
which increases the alkalinity of the water.

Lime-Soda Treatment
The problems: Increased levels of soluble sodium salts in the boiler,
leading to dangers of foaming and carry-over.
Uncontrolled production of sodium hydroxide leading
to increased levels of caustic alkalinity.
Almost constant blow-down is necessary thus making
this type of treatment uneconomical.

Phosphate Treatment
Phosphate treatment is now universally used for all groups
of boiler.
Phosphate treatment is used in conjunction with either
Sodium hydroxide, or Sodium carbonate
How it works: Phosphate (as Trisodium phosphate) reacts with the
scale forming salts to produce non-adhering sludge.
Sodium hydroxide, increases the alkalinity of the water.
Phosphate and Sodium hydroxide react together to
moderate the increase in alkalinity.

Blow down
Chemical treatments produce sludge within the boiler.
It is important that a close check is kept on the total
dissolved solids level within the boiler and that regular
(daily) blow-downs are undertaken to remove sludge and
freshen the water.
If sludge is allowed to build up in the headers of a water
tube boiler it could well impede the thermal circulation
within the generating tubes which could, in turn, lead to
localised overheating and tube failure.

Blowing down

To avoid damage to the valves and the blow down line it is

important to open the valves in the sequence 1, 2 & 3.

Other Chemicals
Sludge conditioning agents:
Disperses the sludge formed by the treatment of water so
that it may be easily removed by blow down.
Synthetic; Starch; Tannin.
Antifoams:
Used to control foaming in the boiler drum thus
preventing carry-over.
Synthetic

Other Chemicals
Antioxidants: Absorb oxygen from the feed and boiler water.
Hydrazine or Sodium Sulphite.
Anti-corrosives: Prevent corrosion damage within the feed
system.
Neutralising amines - neutralise the acid generated by the
solution of carbon dioxide in condensate.
Filming amines - create an oil attracting, water
repellent
film on metal surfaces which is resistant to both carbon
dioxide and oxygen.

Combined Treatments
Combined treatments are available from many different
suppliers (Nalfleet, Drew, Unitor etc) who supply precise
and simple instructions on their use.
For low-pressure boilers, a modern combined treatment
would consist of Disodium phosphate, Sodium carbonate,
with sludge conditioning agents and anti-foams in the
approximate proportions of 3, 4 and 1 by weight
respectively.
For high-pressure boilers a stricter regime is required, with
more control over the reserves of chemical and separate
chemicals are usually supplied.

Alternative Sources
The following chemicals may be used for other purposes on
board ship:Calcium hydroxide - Lime
Sodium carbonate

Use to make mortar

- Washing soda Used as a water

softener

Sodium hydroxide - Caustic soda Used as a cleaning

agent.
Sodium phosphate - Calgon

Used as a laundry
softener.

Any of the above could be used to treat a boiler in an

emergency.

Dosing with Chemicals

Initial treatment.
Whenever a boiler is filled a suitable quantity of the
appropriate chemical treatment should be added.
Chemical treatment should be added at the rate of 0.5 kg
per 1000 kg of water used to fill the boiler.
When a boiler has unavoidably to be filled with hard fresh
water, twice the stated amounts of treatment should be
used.

Dosing with Chemicals

Subsequent treatment during steaming.
During steaming the chemical treatment should be added to
the boiler water in the amounts indicated by the results of
the routine control tests. It is important to maintain a fairly
constant level of dosing on a day to day basis.
For water tube boilers the boiler treatment is injected
directly into the boiler water drum. Feed treatment is dosed
separately.
For fire tube boilers all treatments may be injected into the
feed line supplying the boiler.

Method of applying chemicals

Dosing
funnel

From feed
pump

To boiler

By-pass
Drain

Water Testing
Representative samples should be taken from each boiler
and the feed system every day and tested immediately.
Ideally a sampling line should be set up to each boiler and
run through a cooling coil, in order to enable a continuous
cooled sample to be produced.
Samples should always be filtered to remove discoloration
caused by sludge etc.

pH Test
Using standard pH papers (range 7 12 pH) dipped into a
fresh sample of water, the colour change of the paper is then
compared to a colour chart supplied with the papers.
This test can be carried out both on boiler and feed water.
Only used as a guide. The next test P alkalinity is more
accurate.

P Alkalinity Test
P Alkalinity or alkalinity to phenolphthalein
Take 100 ml filtered sample of boiler water.
Add 10 drops of phenolphthalein the water will turn
pink if alkaline.
Add drops of N/50 standard solution of sulphuric acid
until the sample turns clear.
Calculation:
The ml. of sulphuric acid used x 10 = alkalinity in terms
of p.p.m. calcium carbonate
This test should also be carried out on feed water.

Caustic Alkalinity Test

To test for free caustic alkalinity.
Take 100 ml filtered sample of boiler water.
Add 10 ml barium chloride.
Add 10 drops of phenolphthalein the water will turn
pink if caustic alkalinity is present.
Add drops of N/50 standard solution of sulphuric acid
until the sample turns clear.
Calculation:
The ml. of sulphuric acid used x 10 = caustic alkalinity in
terms of p.p.m. calcium carbonate
This test should also be carried out on feed water.

Chloride Test
Used to determine the amount of chloride (salt)
contamination in both boiler and feed system.
Use the same sample remaining from the P Alkalinity test.
Add a further 2ml of N/50 sulphuric acid.
Add 20 drops of potassium chromate indicator, the
sample will turn pale yellow.
Add drops of N/35.5 standard solution of silver nitrate
until the whole sample just turns reddish-brown.
Calculation:
The ml. of silver nitrate used x 10 = p.p.m. chlorides

Total Dissolved Solids

The total dissolved solids test gives the total level of
chemicals dissolved in the boiler or feed water.
Usually carried out by using a conductivity meter, which
operates on the principle that the conductivity of water will
increase in proportion to the amount of dissolved salts
contained within it. (Pure water is non-conductive.)
Purpose-built meters are temperature compensated and
calibrated to read directly in terms of p.p.m. of total
dissolved solids.

Phosphate Reserve
The more accurate of the phosphate tests is the
vanadomolybdate test, which requires two calibrated tubes: Take a 20ml sample of boiler water.
Add an equivalent amount of vanadomolybdate reagent
and fill one tube with the sample.
Filled the other tube with an equivalent mixture of pure
distilled water and the reagent.
If phosphate is present then the sample will turn yellow.
The change of colour is measured against a standard
shade disk which give a direct reading in p.p.m.
phosphate.

Hydrazine Reserve
Carried out daily where hydrazine is used as an oxygen
scavenger. This test uses two special constructed cylinders
to avoid air contamination of the sample.
Add 15ml of 0.5N hydrochloric acid to each cylinder.
Add a 10ml sample of boiler water to each cylinder and
top up to 40 ml with distilled water.
Add 10 ml reagent to one cylinder only and cap both
cylinders.
After 10 mins compare the colour change using a
calibrated colour disk.

Caustic Corrosion
To prevent caustic attack it is important to monitor the
relationship between the pH and phosphate levels within the
boiler in order to prevent free caustic or excessive sodium
hydroxide over and above amount required to maintain the
necessary alkalinity.
The following graph shows the correct relationship between
phosphate reserve and pH.

Treating Oil Contamination

Keep the boiler steaming and trace the source of
leakage.
Inject phosphate to increase the alkalinity and help
coagulate the oil.
After a time, start a surface scum and continued until all
the oil is removed from system.
Oil dispersant may be used in the feed system, but the
temperature of the feed water may limit the
effectiveness.
Remember: any blow-down as a result of oil
contamination may go overboard and contravene
MARPOL.

Short Term Storage

During short term idle periods one of the following
methods of protection should be used.
Completely fill the boiler with alkaline water containing
sodium sulphite to leave an excess of 200 p.p.m. sodium
sulphite. The water should be raised to boiling point to
to complete the chemical reactions.
Completely fill the boiler with alkaline water containing
hydrazine to leave an excess of hydrazine of at least 25
p.p.m.
The boiler must be completely drained and refilled before
being taken into service again.