BOILER’s OPERATOR HANDBOOK

CHIMEC S.p.A.
WATER TECHNOLOGY UNIT

CHIMEC S.p.A. Water Technology Unit - BOILER’S OPERATORS’ HANDBOOK - 1

Table of Contents.

1. Water Fundamentals........................................................................................................... 5
1.1 Water Sources ..................................................................................................................... 5
1.2 Water Impurities .................................................................................................................. 6
1.3 Measuring Impurities .......................................................................................................... 6
1.4 Self Assessment Quick Test n°1 ..................................................................................... 10
2 Ion Exchange Resins and Water Softening .................................................................... 11
3 Demineralization ............................................................................................................... 14
3.1 Self Assessment Quick Test n°2 ..................................................................................... 15
4 Water Deaeration............................................................................................................... 16
4.1 Self Assessment Quick Test n°3 ..................................................................................... 19
5 Steam Generation ............................................................................................................. 20
5.1 Boiler Blowdown ............................................................................................................... 22
5.2 Self Assessment Quick Test n°4 ..................................................................................... 25
6 Internal Treatments........................................................................................................... 26
6.1 Corrosion in Boilers.......................................................................................................... 26
6.1.1 Galvanic and Acidic Corrosion ........................................................................................ 26
6.1.2 Caustic Corrosion ............................................................................................................. 27
6.2 Treatments Programmes for Internal Deposition........................................................... 29
6.3 Coordinated Phosphate/pH Programme ......................................................................... 30
6.4 Boiler Blowdown ............................................................................................................... 31
6.4.1 Manual Blowdown ............................................................................................................. 31
6.4.2 Continuous Blowdown ..................................................................................................... 31
6.5 Self Assessment Quick Test n°5 ..................................................................................... 32
7 Steam Purity ...................................................................................................................... 33
7.1 Carryover and its Effects.................................................................................................. 33
7.2 Self Assessment Quick Test n°6 ..................................................................................... 35
8 Condensate System.......................................................................................................... 36
8.1 Effects of pH on Corrosion .............................................................................................. 37
8.2 Corrosion Effects of other Contaminants....................................................................... 37
8.3 Chemical Treatments of Condensate Systems .............................................................. 38
8.3.1 Neutralizing Amines.......................................................................................................... 38
8.3.2 Filming Amines ................................................................................................................. 38
8.4 Self Assessment Quick Test n°7 ..................................................................................... 39

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9 Troubleshooting Sheets ................................................................................................... 40
10 Tests’ Answers.................................................................................................................. 43

List of Figures and Tables.

Fig: 1-1: The Water Cycle ............................................................................................................... 5

Table 1-1: Classification of Water Impurities (solid matter)........................................................ 6
Fig: 1-2: Portable conductivity-meter. .......................................................................................... 6
Table 1-2: pH level and water characteristics. ............................................................................ 7
Fig: 1-3: Laboratory bench pH meter. ........................................................................................... 7
Fig: 1-4: Corrosion and pH safe range.......................................................................................... 7
Table 1-3: Common impurities found in fresh water. ................................................................. 8
Table 1-4: Summary of water properties. .................................................................................... 9
Fig: 2-1: Gelular cationic resin. ................................................................................................... 11
Fig: 2-2: Macroporous anionic resin. .......................................................................................... 11
Fig: 2-3: Water softening in Ion Exchanger beds. ..................................................................... 12
Fig: 2-4: Regeneration step in ion exchanger resins. ............................................................... 12
Fig: 3-1: Conductivity and Silica content profile vs. feed processed. ..................................... 14
Fig: 4-1: Boiler’s tube pitting corrosion...................................................................................... 16
Fig: 4-2: Deaeration system: steam vents are visibile. ............................................................. 16
Fig: 4-3: Horizontal tray-type deaerating heater. ...................................................................... 17
Fig: 4-4: Vertical deaerator. Details of spraying devices are visible........................................ 17
Fig: 4-5: Venting (air-out) from a deaerator. ............................................................................... 17
Table 4-1: Common Oxygen Scavengers products. ................................................................. 18
Fig: 5-1: Steam production in boilers, a simplified scheme. .................................................... 20
Table 5-1: Fire Tube and Water Tube boilers. ........................................................................... 20
Fig: 5-2: Deposition on tubes reduces heat transfer to boiler water. ...................................... 21
Fig: 5-3: Baffle plates in the steam drum to improve steam purity. ......................................... 21
Fig: 5-4: Cyclones are used for separation. ............................................................................... 21
Fig: 5-5: Typical steam drum with centrifugal separators; ....................................................... 22
Fig: 5-6: Deposition’s problems in turbines. .............................................................................. 22
Table 5-2: Maximum allowable impurities content in industrial boilers. ................................. 24
Fig: 6-1: Simplified corrosion cell for iron in water. .................................................................. 26
Fig: 6-2: Caustic under-deposit corrosion. ................................................................................ 27
Fig: 6-3: Water circulation and steam generation in clean circuit............................................ 28
Fig: 6-4: Water circulation and steam generation with deposits.............................................. 28

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Fig: 6-5: Forces acting on water-carried particles..................................................................... 28
Fig: 6-6: Clogged tubes due to deposits. ................................................................................... 28
Fig: 6-7: Precipitating/dispersant treatments: untreated and treated precipitated matter. ... 29
Fig: 6-8: Action’s mechanisms of dispersing polymers. .......................................................... 30
Fig: 6-9: pH as a function of residual orthophosphate in different operational conditions. . 30
Fig: 7-1: Attemperation heat exchanger coil in boiler drum. .................................................... 34
Fig: 7-2: Effects of antifoaming agents on steam purity. .......................................................... 34
Fig: 8-1: Complete boilers’ layout. .............................................................................................. 36
Fig: 8-2: Main compounds in boiler’s streams........................................................................... 36
Table 8-1: Reactions taking place in boiler’s streams. ............................................................ 36
Fig: 8-3: Copper corrosion mechanism. ..................................................................................... 37
Table 9-1: Water Pre-Treatments Trobleshooting..................................................................... 41
Table 9-2: Boilers’ Internal Water Troubleshooting.................................................................. 41
Table 9-3: Condensate Circuit Troubleshooting. ...................................................................... 42

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1. Water Fundamentals 1.1 Water Sources
Pure Water is colourless, tasteless All water Sources originate by

and odourless; its chemical formula is evaporation from terrestrial and oceanic

H2O; this means that one molecule of masses, followed by rain and snowfall.

water, is formed by two atoms of While raining, water droplets enter in

Hydrogen and one of Oxygen. contact with dissolved gases in the

Water is fundamental for Life (see atmosphere, but also with suspended

Fig 1-1), and it covers four fifth of the particles, dust, smog and other

Earth’s surface; industrially-originated pollutants.

The two most important sources of

Fresh Water are surface water and
ground water.
Water flowing in rivers, varies in
composition according to the ground’s
characteristics.
Ground water is characterised by a

Fig: 1-1: The Water Cycle relatively constant temperature and a

lower level of suspended solids; these are
Water has different properties such properties highly desirable in industry.
as that of being able to dissolve partially, On the other hand, ground water has
almost any substance found on earth or a higher level of dissolved solids
atmosphere; for this reason, water is (minerals) respect surface water.
called the universal solvent.
Although there is abundance of Recycled water and sea water
water, it is not readily available in the represent another source; the first must
conditions we desire for industrial needs. be used for economical and
Water used in industry, in fact, environmental reasons, the latter for
contains impurities, responsible for cooling systems only (if more economical
problems such as deposition in pipes, alternatives do not exist).
conduits, Boilers’ tubes and others.

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1.2 Water Impurities content of minerals) has a much higher
conductivity.
Impurities (solid matter) in water,
Conductivity is easily measured by a
vary in quantity and nature too.
Conductivity-Meter, and is expressed in
They depend on water sources and
can be defined as shown in Table 1.2-1. µS/cm.
Fig. 1.2 shows a portable
Table 1-1: Classification of Water Impurities
(solid matter). conductivity-meter.
Suspended Solids Refers to Undissolved
- SS- Matter in water
Refers to the Total amount
Dissolved Solids
of dissolved matter in
- DS-
water
Total Solids Refers to the sum of DS
- TS - and SS
Dissolved Gases Refers to the gases
- DG- Dissolved in water

All waters contain variable Fig: 1-2: Portable conductivity-meter.

concentrations of dissolved salts, that are

A common, and useful unit to
likely to dissociate in charged particles
express concentration of impurities in
called ions.
water, is ppm (parts per million).
Cations are positive, anions are
It expresses the amount, in mg of a
negative; the chemical equation below
substance, in 1 kg (1 Liter) of water.
shows dissociation of NaCl (sodium
Its submultiple, ppb (parts per billion)
chloride) in water:
expresses the amount in µg, and is used
NaCl → Na+ + Cl-
to determine traces of substances.
Useful information on water
1.3 Measuring Impurities characteristics can be obtained by
Conductivity measures the ability knowing the value of the pH.
of an aqueous solution to carry an electric pH ranges from 0 to 14 with
current. neutrality at 7.
Different waters have different Neutrality means that the amount of
conductivity levels: distilled water (nearly H+ ions is the same as that of OH-.
pure water as H2O), carries little Acidity occurs at pH lower than 7,
electricity, whereas sea water (higher Basicity at pH higher than 7.
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 Table 1-2 summarizes pH level and The picture below, shows the safe
Water characteristics. pH range to be kept in the water to avoid

Table 1-2: pH level and water characteristics. corrosion.

pH value Water Characteristics

pH < 7 Acidity
pH = 7 Neutrality
pH > 7 Basicity

Usually, natural waters have a pH

between 6 and 8; it is possible to modify
the pH of a given water, by adding acid or
alkaline substances.
For example, the addition of H2SO4
(sulphuric acid) will contribute with H+
ions in water, lowering the pH.
The addition of NaOH (caustic
soda), will, instead, contribute with OH-
Fig: 1-4: Corrosion and pH safe range.
ions to raise the pH.
pH is easily measured by a pH-
As we can see from Fig. 1-4, the
meter: a laboratory device is shown in
safe range of pH is between 8.5 and 12.7.
Fig. 1-3 below.
This range should be carefully taken
into account by operators while operating
a boiler.

The tables below (Table 1-3 and 1-

4) summarize many aspects and
problems due to the presence of common
species in water.
Fig: 1-3: Laboratory bench pH meter.
They help familiarize with common
water-related terms.
Low or high pH may cause corrosion
in boilers and in boilers’ systems.

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Table 1-3: Common impurities found in fresh water.

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Table 1-4: Summary of water properties.

Common and routine analyses are

based on titration methods; for more
precise results, photometer based or
other techniques measures are preferred.

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1.4 Self Assessment Quick 6) Water with a pH of 3.5
Test n°1 is……………………, water with a pH
of 10.5 is ……………………
This test has been designed to help
the Reader familiarize with common
terms of water and in operational
conditions.

The Reader should fill the gaps with

the appropriate terms:

1) As Water is able to dissolve almost

any substance, it is called
……………………………………………

2) The two sources of fresh water

are……………………………….and…
…………………………………………..

3) The impurities found in water are

classified as:……………………solids,
…………………………………….solids
and……………………………….gases.

4) The unit measure of conductivity

is:…………………………………………

5) The transition between Acid and

Alkaline Water is determined by
measuring the…………………………..

(See end of handbook for answers)

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2 Ion Exchange Resins and
Water Softening
Ion exchange is a process by which,
some substances exchange an ion,
present in water, with another.
This exchanged ion, is then released
back by a regenerating solution, as the
exchanging capacity of the system
reaches very low values. Fig: 2-2: Macroporous anionic resin.
This process applies better for the
removal of dissolved solids. Resins do exist for the removal of
Nowadays, the most used mediums cations and anions dissolved in water.
for ion exchange are resins. The most useful application of
exchange resins is the softening of water:
Resins are usually spherical in this means that calcium Ca++ and
shape to maximise the surface contact magnesium Mg ++
ions, are replaced
between water and the ions to be (exchanged) with other cations, usually
exchanged. sodium Na+.
Fig. 2-1 and Fig. 2-2 show two types Calcium and magnesium are
of ion exchange resins. responsible for water hardness; these
cations, in fact, react and form
precipitates with other ions in water, to
form scale in boilers (mainly as CaCO3
and MgCO3).
For this reason, water softening is
always necessary for boilers systems.

As shown in Fig 2-3: raw water

enters from the top, softened water
leaves from the bottom.
Fig: 2-1: Gelular cationic resin.

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Fig: 2-3: Water softening in Ion Exchanger
beds.

In order to ensure a continuous

cycle, an operating system is always
coupled by a regenerating system. Fig: 2-4: Regeneration step in ion exchanger
resins.

Regeneration takes place as the ion

Mixed bed resins unit, as shown in
exchange capacity of the resin reaches
Fig 2-4, are often positioned at the end of
very low levels.
a demineralization system.

A concentrated solution, (acid or

As they contain both types of strong
alkaline for cationic and anionic resins
resins, they work like a large number of
respectively), washes back the ion
cationic and anionic resins in series;
exchangers tanks and restores the initial
this ensures a superior water quality
conditions.
as any anionic site captures immediately
the acid produced by the cationic site.
After regeneration, slow and fast
rinsing follow.
The major benefits coming from well
These two processes, ensure the
managed ion exchanger unit are the
complete regeneration of the units.
following:
1) treated water has little trend to be
Fig 2-4 shows the complete process
encrusting. This is due to the
of regeneration.
hardness level reduced below 2 ppm.
2) Easy and automated process

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3) Regeneration is easy to manage and
safe to handle.
4) Waste water shows little, or no impact
on environment.
5) Feedrate variations usually are well
tolerated.

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3 Demineralization Fig. 3-1 shows a typical operational
cycle:
The demineralization process
removes all the inorganic salts dissolved
in water, producing pure water.
Demineralization plants consist of
two or more tanks of cationic and anionic
resins.
The first step is a cationic resin that
releases H+ ions in water and adsorbs Fig: 3-1: Conductivity and Silica content
profile vs. feed processed.
undesired ions, such as Ca++, Mg++ and
Na+.
Effluent silica and conductivity are
The second step, following the first
important parameters to monitor; both
2− -
one, removes anions such as SO , Cl , 4 silica and conductivity are low at the end
2− − -
CO , NO releasing OH in water.
3 3 of the rinse; often conductivity decreases
Acid exchange, converts salts in momentarily, and this is explained by the
their corresponding acids, so small level of sodium hydroxide produced
bicarbonates, sulphates and chlorides in the anion exchanger.
turn in carbonic, sulphuric and When silica breakthrough occurs,
hydrochloric acid respectively. the sodium hydroxide converts into
Weak Anionic units eliminate sodium silicate which is less conductive.
sulphate and chloride ions, whilst, strong
anionic resins remove carbonic acid and When the end of a demineralizer run
silicates. is detected, the unit must be removed
Regeneration, (see Fig 2-4) at the from service immediately.
end of a cycle, is carried out by using
strong acids or bases feeds in strong (or It is wise to remind that the resins
weak) resins. are susceptible to suspended solids and
organic substances, acting as fouling
Conductivity is constantly measured agents leading to system’s clogging.
in the system and as soon as it reaches
specific values, regeneration starts or is
interrupted;

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3.1 Self Assessment Quick
Test n°2

1. Demineralization consists of two

steps; the first one converts dissolved
salts in their corresponding……………

2. The acids produced in the cationic unit

are then removed into
the…………………………unit.

3. Conductivity is almost constant during

service; close to the end of the cycle,
it………………….momentarily and
then…………………rapidly.

4. Cationic resin is regenerated

by…………….., anionic resins is
regenerated by……………………….

5. A mixed bed consists of both types

of………………….cationic and anionic
resins.

(See end of handbook for answers)

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4 Water Deaeration Solubility is a function of the partial
pressure of a gas in a liquid medium;
Water contains dissolved gases as the higher the partial pressure, the
well as suspended and dissolved solids. larger the quantity of the gas that is
As solids are removed in dissolved in the liquid.
demineralization units, gases must be Also the temperature influences
eliminated. solubility (as stated in Henry’s Law), and
Oxygen causes severe corrosion the higher the temperature the lower the
(see Fig 1-4) in boilers called pitting. solubility.
Pitting is a localized corrosion By knowing these concepts,
phenomena and may lead to system’s deaeration can take place by either
failure; lowering the pressure or raising the
Fig 4.1 shows a boiler’s tube temperature of the system;
attacked by oxygen pitting; further details The medium used for deaeration is
will be given later. steam, as it raises the temperature and,
as it enters the system, lowers the partial
pressure of the gas. Furthermore, it does
not pollute the water being treated, and is
readily available in industrial plants.
Fig 4-2 shows a deaerator in an
industrial site. Note the tank under the
deaerator device that collects the
deaerated water.
Fig: 4-1: Boiler’s tube pitting corrosion.
Water containing ammonia causes
corrosion in copper and its alloys.
The most used method for gases
removal is the deaeration.
Before going further into dearation, it
is useful to introduce the concept of
solubility as it is strictly related to the
deaeration processes:
Fig: 4-2: Deaeration system: steam vents are
visibile.

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 Fig 4-3 shows constructive details of A tray-type deaerator consists of a
a horizontal “tray-type” deaerating heater
tank, an inlet pipe for water distribution
and Fig 4-4 shows details of a vertical
and a series of trays.
deaerator.
The working mechanisms is that as

follows: water enters the system by the

inlet pipe and meets a steam

atmosphere; at these conditions, oxygen

and carbon dioxide leave water. In the

trays’ section, water is divided into fine

droplets, resulting in maximization of the

surface’s contact.
Fig: 4-3: Horizontal tray-type deaerating
heater. It is necessary, for a correct

management, to provide adequate

venting of the system (see Fig 4-5);

usually, a 50 to 100 cm of air-out is

recommended.

Fig: 4-4: Vertical deaerator. Details of spraying

devices are visible. Fig: 4-5: Venting (air-out) from a deaerator.

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 Deaerators systems require little
maintenance, provided that influent water
contains no suspended solids, as well as
hardness and alkalinity, that may lead to
sprayers clogging.
Suppliers normally ensure
oxygen residue content of circa 7 ppb,
that is still unacceptable for boilers
operating conditions.
This means that chemical deaeration
is necessary; in this case deaeration is
called oxygen scavenging.
The common products used as
oxygen scavengers are summarised in
Table 3.1-1 here below.
Other chemical used as oxygen
scavenger are hydrazine, hydroquinone.
These chemicals are being phased
out for health and safety reasons.
Carbon dioxide gas CO2 will leave
an the system together with oxygen;
it exists dissolved in water to form
carbonic acid that lowers water pH.
At the boiler’s working conditions,
carbonic acid releases CO2 responsible
for acid corrosion in condensate lines;
for this reason protective/filming or
neutralizing chemicals such as amines,
will be added.

Table 4-1: Common Oxygen Scavengers

products. It is wise, now, to draw the
Chemical Notes operators’ attention to the importance of a
Sodium Max Pressure 42 Bar. Contributes clean water entering the deaerator, as
Sulfite1 to solids content and conductivity
well as an adequate retention time.
No Pressure limits. No contribution
to solids content or conductivity.
DEHA2
Promotes a protective magnetite Retention time is usually between 10
layer.
Ascorbic No contribution to solids content or and 20 minutes and this time ensures the
or Erithorbic conductivity.
acid3 Passivating properties reactions of oxygen removal to complete.

1
Inorganic Sodium Sulfite reacts with Oxygen as
follows:
2Na2SO3 + O2 = 2Na2SO4.
Residue is easy to analyze. Suitable for Wet
Storage and approved by the FDA for
Food/Pharmaceutical Processing.
2
Organic Diethylhydroxylamine; residue is easy to
analyze. Suitable for Wet Storage
3
Organic Ascorbic or Erithirbic Acid: suitable for
steam used in Food Processing or
Pharmaceuticals. Not suitable for Wet Storage.

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4.1 Self Assessment Quick
Test n°3
1. Water containing dissolved solids
causes corrosion;
Pitting corrosion is originated by
…..………………..; acid attack in
condensate lines is caused
by…………………………..; copper
and its alloys are corroded
by…………………………

2. Solubility of a gas into a liquid is

directly related to the
………………………….of the gas.

3. The higher the temperature of the

liquid, the………………………the
concentration of the gas in the liquid.

4. Steam is used in Deaerators because

it:
a. ……………………………..
b. ……………………………..
c. ……………………………..

5. Inlet water must be free from

………………………….solids

6. Oxygen traces must be removed by

using………………………………such
as…………………….,…………………
……………….and…………………….
(See end of handbook for answers)

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5 Steam Generation Boiler’s Working
Comments
Type Principle
High potential
Water flows in
Steam has always been used for by 4 system, Steam
Water Tube tubes exposed
Production > 100
to heat
mankind; its main purposes are T/h
Low potential
Water is
production of energy in boilers and Fire Tube5 surrounded by
system, Steam
Production < 20
turbines systems, heating medium and hot tubes
T/h

many other applications.

At normal pressure conditions, 1
Atmosphere, water boils at 100°C; these
Fig 5-1 shows a simplified scheme
conditions would have little interest for
for steam production.
industrial steam applications.
For this reason, the system’s
pressure, and its related temperature, is
usually much higher; common pressures
and temperatures-ranges, vary from 5 to
150 Bar.

The energy required by water to turn

Fig: 5-1: Steam production in boilers, a
simplified scheme.
As it can be seen in the picture, heat
is provided to feed water, entering the
Lower Drum and steam leaves the
system from the Upper Drum.
Before going into further details, it is
wise to highlight the two main building
characteristics of a boiler, as they are
related to the way by which steam is
produced (Table 5-1):
Table 5-1: Fire Tube and Water Tube boilers.
into steam, is provided by the burning of
fuels such as oil, gas or coal.
Burning fuels release energy (heat
and light mainly) to water, by means of
the exchangers’ surfaces, either by
convection or radiation.
Deposits, both in water or fire side,
will make the system require more energy
for the same steam production, as they
lower the heat transfer capacity.
4
Water becomes steam in the tube itself as it is in
contact with hot fumes.
5
Hot fumes’ tubes are immersed in water and
steam is produced.

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 Too high temperatures on tubes’
walls, may lead to tubes’ breakdown and
system’s failure; see Fig: 5.2 for details.
Common devices such as cyclones,
centrifuges are found as shown in Fig 5-3
Fig 5-4 and Fig 5-5 (typical steam/water
separation line is visible).
.

Fig: 5-2: Deposition on tubes reduces heat

transfer to boiler water.

As we have learnt, deposits are

caused by solids present in water, so, the
higher (and critical) the working
Fig: 5-3: Baffle plates in the steam drum to
conditions, the lower the content of the improve steam purity.
impurities allowed.

Boilers are defined as Natural

Circulation as the cold feed water,
heavier than hot water, flows from the
Upper Drum down to the Lower Drum and
viceversa.

Tubes in the “cold-side” are called

Downcomers, those belonging to the “hot-
side” are the Upcomers.

In order to prevent the steam to

carry away water droplets, steam-water
Fig: 5-4: Cyclones are used for separation.
separators (drift eliminators) are installed
in the upper side of the boiler.

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 The steam leaving the system is
saturated steam and, in order to raise its
temperature, superheaters are used.

Superheaters, provide additional

heat as they are much closer to the
burners;
Superheaters collect radiant heat to
be transferred to water, and make the
Fig: 5-5: Typical steam drum with centrifugal
separators; steam suitable for driving turbines.
Once again, feedwater quality is
Separation of water from steam, is fundamental for correct and safe
always necessary for turbines systems, operations in boilers’ systems.
as water droplets cause serious
mechanical damages on blades. 5.1 Boiler Blowdown

Fig 5-5 shows a turbine forced off- While water is being turned into

line for deposition due to inadequate steam, impurities present at very low

steam separation. concentrations are kept in the liquid

phase;
As more and more steam is
produced, from the same amount of
water, impurities may reach precipitating
conditions.
This will result in deposits’ growth
so, removal of solids is mandatory, and
this action is called blowdown.
Fig: 5-6: Deposition’s problems in turbines.

Continuous or intermitted blowdown

Furthermore, Silica, found in steam,
avoids precipitation of solids and is the
causes hard deposits on blades so, its
characterizing factor of a boiler.
elimination in the demineralising unit, is a
critical need.

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 Number of Cycles “Nc”, identifies the
FeedWater to Blowdown Ratio6.

It is fundamental to get a high

number of cycles, as it is also related to
operational performances, and energy
savings.
The higher the Nc the lower the
blowdown.
Table 5.2, summarises the
maximum content of impurities that may
be allowed in the system.

It is wise to note that as the

conditions (pressure and temperature)
get harder, the limits reach very low
levels of acceptability.

6
Nc may range from 5 up to 150 for very high
Pressure systems.

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Table 5-2: Maximum allowable impurities
content in industrial boilers.

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5.2 Self Assessment Quick 8. The Nc identifies the ratio
Test n°4 between…..………..and..…………….

9. The higher the Nc the…………….the

1. The heat transfer from tubes to the
Blowdown.
surrounding water, characterizes
…………………………boilers.

2. The heat transfer to water in tubes

characterizes…………………..boilers.

3. The heat transfer in a boiler takes

place by means of two main
mechanisms:
……………………and…………………
….. .

4. Colder, relatively heavier Water flows

…………into the………….………whilst
warmer water flows…………….into
the…………………. This characterizes
the………………circulation systems.

5. An additional heat is provided to

saturated steam by…………………….

6. The phenomena of solid content

increase, is controlled by continuous
or intermitted……………………

7. The acceptable limits of impurities

get………………….as the conditions
get harder. (See end of handbook for answers)

CHIMEC S.p.A. Water Technology Unit - BOILER’S OPERATORS’ HANDBOOK - 25

6 Internal Treatments
As previously discussed,
quality is fundamental for a correct and
safe operational management of a boiler
system.
Table 5-2 provided recommended
limits at various conditions.
These limits apply mostly for the
impurities responsible of corrosion and
deposition such as metal
hardness and silica.
6.1 Corrosion in Boilers
Corrosion in boilers causes serious
risks of failure, including tubes and
surfaces spoiling/breakdown and even
explosions.
There are three main types of
corrosion, for which several impurities
maybe responsible:
⇒ Galvanic Corrosion
⇒ Acidic corrosion
⇒ Caustic corrosion
6.1.1 Galvanic and
Corrosion
Galvanic corrosion occurs when a
metal, or alloy, is electrically coupled to a
different metal alloy.
CHIMEC S.p.A. Water Technology Unit - BOILER’S OPERATORS’ HANDBOOK -
In a boiler, galvanic corrosion is
caused by the contact of different metals,
water
such as iron and copper.
These differential cell, can be
formed when deposits are present and
also at the welds, due to stresses in heat-
affected zones, or due to the use of
different alloys in welded parts.
oxides,
Fig: 6-1: Simplified corrosion cell for iron in
water.
As seen already in Fig 4-1, oxygen
removal is fundamental to avoid pitting
corrosion; not only oxygen causes
corrosion, but other impurities do, like
salts whose hydrolysis is acidic.
For example, if Mg2+ and Cl2- were
not eliminated in the demineralising unit,
they would form MgCl2 salt; then the
following reaction takes places in water:
MgCl2 + H2O = Mg(OH)2 + 2HCl
Acidic
leading to acid conditions in the boiler
water.
Hydrochloric acid previously formed,
dissolves magnetite,
26
6.1.2 Caustic Corrosion
The specific requirements for water
high quality, are related to the need of
ensuring an appropriate pH in alkaline
ranges, including
⇒ buffering properties
and
⇒ the ability of neutralizing caustic
soda corrosion.
Caustic soda corrosion, occurs as
the boiler water can become highly
concentrated, via iron oxide deposition on
tube surfaces.
Iron oxide deposits are often quite
porous and act as miniature boilers (see
Fig 6-2).
At these conditions, it is possible to
have 100,000 ppm of caustic beneath the
deposit, while the bulk water contains
only about 5-10 ppm of caustic.
CHIMEC S.p.A. Water Technology Unit - BOILER’S OPERATORS’ HANDBOOK -
Fig: 6-2: Caustic under-deposit corrosion.
The chemical reaction here below,
takes place in boiler water, in presence of
sodium-phosphate-based products:
Na2HPO4 + NaOH → Na3PO4 + H2O
In other words the reaction states
that Disodium Phosphate reacts with
Sodium Hydroxide to produce Trisodium
Phosphate and Water.
This, results in neutralization of
caustic and minimization of materials
corrosion and embrittlement, due to
caustic build up beneath deposits or
within a crevice.
Deposition and its effects on flow
and heat transfer are shown in Figs 6-3 -
6-6.
27
 function of water sweep as well as
surface charge (see Fig 6-5);

If the circulation is not adequate to

provide enough water sweep, the particle
may adhere on tube’s walls, leading to
overheating, inadequate formation of
steam and mechanical stress.

Fig: 6-3: Water circulation and steam

generation in clean circuit.

A clean, deposits-free tube, ensures

the optimal flow and heat transfer, as well
as adequate conditions for steam/water
mixture formation.

Fig: 6-5: Forces acting on water-carried

particles.

Fig: 6-4: Water circulation and steam

generation with deposits.
Fig: 6-6: Clogged tubes due to deposits.

Circulation and deposition are

closely related; deposition of particles is a

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6.2 Treatments Programmes
for Internal Deposition
The two most used technologies for
boilers’ internal treatments
classified as follows:
⇒ Solubilizing/Dispersant Treatments
⇒ Precipitating Treatments
The solubilizing treatments, were
commonly used in the past.
These limits are now overcome by
using both precipitating/dispersing
treatments.
Precipitating/dispersant treatments,
can be based on phosphates and polymers
technology, are now commonly found in
high pressure boilers.
They promote precipitation of both
metals oxides and hardness, responsible
for scaling.

These precipitates, are in the form of

The use of chelating agents, able to
incoherent matter, that can be easily
solubilize the contaminants, that would
eliminated by Blowdown as they show
otherwise precipitate, has now been
limited adherence on tubes’ walls
replaced by precipitating/dispersing
(dispersant action).
treatments.
Impurities such as hardness, were
Fig 6-7 shows untreated (Left-
kept in suspension but, the chelating
leading to deposition) and treated (Right-
agents, did have the ability to solubilize
crystals do not aggregate) precipitated
also the metals of the system, leading to
particles in boiler’s water.
failures.
Furthermore, difficulties on dosages
and control, made this technology not
reliable.

Precipitating treatments, mainly

based on phosphates, are highly effective
on hardness cations; however, they show
little action on metal oxides, also Fig: 6-7: Precipitating/dispersant treatments:
untreated and treated precipitated matter.
responsible for deposition.

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 Fig 6-8 shows a simplified action’s Depending on specific operating
mechanisms of dispersing polymers. needs, pH buffering is enhanced by
choosing a low Na/PO4 Ratio, usually
closer to 2.2 (all disodium).

To achieve a higher caustic

neutralization capacity, a ratio closer to 3
(all phosphates) should be preferred

Fig: 6-8: Action’s mechanisms of dispersing instead.

polymers.

6.3 Coordinated Phosphate/pH

Programme
A more advanced treatment
programme, is achieved by the
Coordinated Phosphate/pH.
Fig: 6-9: pH as a function of residual
orthophosphate in different operational
By using internal treatments’ conditions.
Phosphates-based products, caustic
corrosion and caustic embrittlement do Overall program control is
not occur, because high caustic achieved by feeding the proper mix of
concentrations do not develop and pH is phosphate, to either raise or lower the
kept at the optimal level. pH, while maintaining the proper
phosphate level.
Fig 6-6 shows the recommended
concentration of residual orthophosphate, Increasing blowdown lowers both
necessary to keep the appropriate pH in phosphate and pH, therefore, various
the system. combinations and feed rates of
It takes into account also the phosphate, blowdown adjustment, and
sodium/phosphates ratio to choose, while caustic addition are used to maintain
considering boiler’s operating pressure proper phosphate/pH levels.
and temperature (see Fig. 6-6).
CHIMEC S.p.A. Water Technology Unit - BOILER’S OPERATORS’ HANDBOOK - 30
 Phosphate-based products are 6.4.2 Continuous Blowdown
nowadays fully integrated with dispersant
Continuous blowdown offers many
polymers, whose function is to keep solid
advantages not provided by the use of
deposits (oxides, sludges, etc.) in
bottom blowdown.
suspension to avoid build up in the
system.
Water may be removed from the
location of the highest dissolved solids in
6.4 Boiler Blowdown the boiler water.
Blowdown, as previously discussed, As a result, proper boiler water
is fundamental for a correct operating quality can be maintained at all times.
management of the boiler;
two main blowdown’s systems exist: When continuous blowdown is used,
manual blowdown is limited to
⇒ Manual Blowdown
approximately one short blow per shift to
⇒ Continuous Blowdown
remove suspended solid, which may have
settled near the blowdown connection.
6.4.1 Manual Blowdown
Manual blowdown is designed to
remove suspended solids, including any
sludge formed in the boiler water.

The manual blowdown is usually

located at the bottom of the lowest boiler
drum, where the sludge would settle.

In practice, manual blowdown valves

are opened periodically in accordance
with an operating schedule.

Frequent short blows are preferred

to infrequent lengthy blows.

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6.5 Self Assessment Quick
Test n°5

1. The internal treatments are necessary

to prevent …………………..of solid
matter in the boilers.

2. Particle’s deposition in tubes, is

closely related to the
water……………………

3. Deposition in tubes affects regular

formation of…………………………

4. The main internal treatments’

programmes are:
……………………and…………………

5. Impurities such metals oxides were

not effectively removed
by………………………..treatments.

6. Phosphates are the base for

……………….treatments.

7. ……………………..treatments are
nowadays fully integrated
by………………..polymers.

8. Precipitated particles are in the form

of………………………..matter that will
be easily removed by………………….. (See end of handbook for answers)

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7 Steam Purity
Chapter 5 describes steam
production and the major operations
required for high quality of steam.
This chapter focuses on specific
requirements to ensure a high purity
steam.
As described earlier, precise system
control for modern superheated steam
turbines is necessary; solids in steam
leaving the boiler, can deposit in
superheaters and turbines.
Steam purity refers to the amount of
solids, liquid or vaporous contamination in
the steam.
Steam purity should not be confused
with steam quality, as it is referred to the
amount of moisture in steam.
For example, steam of 99% quality
contains 1% of liquid water.
Carryover is any solid. liquid or
vaporous contaminant, that leaves a
boiler steam drum with steam.
The entrained boiler water, contains
dissolved solids and can also contain
suspended solids.
There are many causes of water
entrainment, some have been given a
specific name such as:
⇒ Spray Carryover
⇒ Leakage
⇒ Foaming
CHIMEC S.p.A. Water Technology Unit - BOILER’S OPERATORS’ HANDBOOK -
7.1 Carryover and its Effects
Dissolved solids and suspended
solids in steam form deposits in nonreturn
valves, superheaters and turbines.
Carryover is responsible for
contamination of process’ streams and
affects product’s quality.
Carryover results from incomplete
separation of steam from the water-steam
mixture.
Superheated steam turbines are
particularly prone to damage (and failure)
by carryover.
Many factors contribute to
incomplete separation, either chemical or
mechanical.
Mechanical causes may refer to
boilers’ design, working pressure, steam
drum size, generating rate, arrangement
of downcomers and risers and so on.
An appropriate water and steam
separation device is fundamental (as
seen in Fig 5.5).
Steam can be contaminated with
solids, even where carryover is not
occurring;
contaminated spray-attemperating7
water can introduce solids in steam.
7
Attemperating water is used to control
superheaters temperature at the turbine inlet.
33
 To avoid attemperating water of oil and detergents in feedwater
injection, a heat exchanger coil may be enhance foaming.
placed in the boiler drum, as shown in Fig The addition of antifoaming agents,
7-1. helps increase the maximum allowed
solid content, as shown in Fig 7-2.

Fig: 7-1: Attemperation heat exchanger coil in

boiler drum.
Fig: 7-2: Effects of antifoaming agents on
steam purity.
It is wise to remember that the mud
drum is at higher pressure than Control and management of
superheated steam, and this may lead to carryover and foaming, is based on either
contamination, if leakage occurs. increasing the blowdown rate (to
eliminate excess of solids), or the use of
Foaming is the stable formation of chemical internal treatments together with
bubbles in boiler water; antifoaming agent, (for foam control).
Because bubbles have a density
close to that of steam, they are not readily These control methods cannot be
removed by steam purifying equipments. always considered effective, as the
Furthermore, foaming is responsible content of solids’ limit, cannot be
for common erroneous water-level generalized.
readings, leading to unstable adjustments
in feedwater flow. However, the best method for a
more effective control, is to keep the solid
Foaming tendency of a boiler water contents as low (close to zero) as
increases as the alkalinity and solid possible.
contents increase; not only these
substances contribute to foaming; traces

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7.2 Self Assessment Quick contribute to …………….deposition
Test n°6 on turbine’s blades.

1. The purity of steam refers to the

solid, liquid and vapour impurities in
steam; the measure of humidity in
steam, is called………………..and
should not be confused with steam
purity.

2. Any contaminant leaving the system

causes…………………..to in the
steam phase.

3. Mechanical causes for carryover

include…………………….……of the
boiler, ………………………..devices,
…………………..levels of water in
the upper cylinder body and
………………….conditions of the
whole system.

4. Alkalinity and organic substances in

boiler water, are the
…………………………..causes for
carryover .

5. ……………………is the most

influencing factor for Chemical
carryover.

6. ………………………….water for
temperature control in turbines can (See end of handbook for answers)

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8 Condensate System As the feedwater contains
carbonates (CO3=) and bicarbonates
Once steam has been produced and -
(HCO3 ), they will end up in the two other
distributed along the plant, the
streams;
condensate re-enters the boiler system;
In particular, hydroxyl compounds
As it can be seen in Fig 8-1,
will preferably exist in blowdown, while
feedwater (FW), blowdown (BD) and
carbon dioxide gas will leave the system
condensate circuit (C) constitute the
by going into the condensate lines.
whole boiler system.

At boiler’s working conditions the

reactions in Table 8-1 will occur:

Table 8-1: Reactions taking place in boiler’s

streams.

Stream Reactions

2HCO3- → CO3= + H2O + CO2

Fig: 8-1: Complete boilers’ layout. Feedwater
CO3= + H2O → 2OH- + CO2

CO2 + H2O → H2CO3

Makeup water (MU) takes into H2CO3 → H+ + HCO3-
Steam
account system’s losses and, Fe + 2H+ → Fe2+ + H2
consequently, the lower the losses, the 2Cu + 2H+ → 2Cu+ + H2 (§)

lower the makeup water needs. Blowdown OH-

Fig 8-2 shows the main chemical

compounds present in each boiler Consequence of carbon dioxide

stream; (CO2) presence in the condensate lines,

is pH lowering and corrosion, both on iron
and copper metallic systems.

Fig 8-3 shows copper corrosion

mechanism;

§
Fig: 8-2: Main compounds in boiler’s streams. These reactions, responsible for corrosion of
metallic iron and copper, result from carbon
dioxide, leading to formation of carbonic acid and
hydrogen ions.

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 Oxides of copper, unlike iron oxides
are porous and leaky, allowing water,
oxygen and copper ions to move to and
from metal surface.
Fig: 8-3: Copper corrosion mechanism.
8.1 Effects of pH on Corrosion
the boiler and released into the steam (as
seen in Table 8-1 reactions).
Low pH causes generalized loss of
metal, rather than localized pitting due to
oxygen corrosion; pipe walls are thinned,
particularly at the bottom of the pipe.
In order to reduce low pH-induced
condensate system corrosion, it is
necessary to lower the concentration of
acidic contaminants.
Less feedwater alkalinity means less
carbon dioxide in steam and condensate.
Venting, at certain points of the
condensation lines, can be effective in
CO2 removal.

The stability of passivated iron and

copper is critically dependent on 8.2 Corrosion Effects of other
condensate pH. Contaminants
Any contaminant in the condensate When pH is correctly maintained in
system, that causes pH to decrease, the system, other contaminant may affect
leads to dissolution of the protective oxide corrosion rates of iron or copper.
layer and increases corrosion. Contaminants like chlorides,
sulfides, acetates and ammonia (for
Carbon dioxide CO2 is the primary copper) can dissolve protective layers.
cause of decreased condensate pH.
CO2 may enter the system with air Ammonia is the most common
leaking into the condenser, or from contaminant, and is usually present at
decomposition of feedwater alkalinity. very low concentrations;
Although part of the feedwater it results from breakdown of
alkalinity is removed properly by internal nitrogen-based organic contaminants, but
treatments, most is converted to CO2 in can also be used carefully to control
condensate pH.

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8.3 Chemical Treatments of ⇒ Distribution ratio DR8 refers to the
Condensate Systems capacity of the amine to exist both in
liquid and steam phases in the
Condensate systems can be
condensate lines.
chemically treated to reduce metal
Neutralizing amines, must be
corrosion.
chosen accordingly to their distribution
Commonly used Chemical Products
characteristics to chase the acidic
treatments include:
contaminants.
⇒ Neutralizing Amines
⇒ Filming Amines
8.3.2 Filming Amines
and Oxygen Scavenger/metal passivator
Another approach, for condensate
8.3.1 Neutralizing Amines corrosion control, is the use of chemicals
that form a protective film on metal
Neutralizing amines are used to
surfaces.
neutralize the acid (H+), generated by the
Filming amines protect against
dissolution of carbon dioxide (and other
oxygen and carbon dioxide corrosion, by
contaminants), in the condensate.
replacing the loose oxide scale on metal
By regulating the neutralizing amine
surfaces, with a very thin amine-film
feed rate, the pH of condensate can be
barrier.
raised to within a desired range.
Neutralizing amines are further
For maximum efficiency, blends of
characterized by other important
filming amines, should be fed directly to
parameter like neutralizing capacity,
the steam header.
basicity, distribution ratio and thermal
stability.
Oxigen-scavenger and metal
⇒ Neutralizing capacity, is the
passivator chemicals, provide both
concentration of the acidic
removal of oxygen, responsible for
contaminant, that is neutralized by a
corrosion, and promote formation of
given concentration of amine.
protective layers on metals’ surfaces.
⇒ Basicity refers to the ability of an
amine, to “hydrolize” in water and
boosting pH after acids’
8
neutraliztion. DR = Amine in Vapour Phase / Amine in Liquid
Phase. DR > 1 means more amine in vapour phase.

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8.4 Self Assessment Quick .
Test n°7 7. Neutralizing amines can be fed in
several points of the system
1. The two most common contaminant,
(feedwater, upper cylinder body)
responsible for corrosion in
while filming amines are dosed in
condensate systems are
the…………………………….
…………………..and…………………
.
2. Carbon dioxide forms in condensate
lines because of decomposition
reaction of……………………….

3. Oxygen may enter the system due to

losses in the……………………..and
for inefficiency in the………………..

4. Chemical treatments for condensate

lines are mainly based on
………………………….: in particular,
their working principles are:
a. ……………… amines
b. ……………….amines
and oxygen……………/passivators

5. The main characteristics for

selecting neutralizing amines are:
a. …………………..capacity
b. ………………………..
and ………………………….ratio

6. To keep into account the above

mentioned characteristics,…………..
of filming amines are used.
(See end of handbook for answers)

CHIMEC S.p.A. Water Technology Unit - BOILER’S OPERATORS’ HANDBOOK - 39

9 Troubleshooting Sheets
The information here in presented,
are intended only as a support for boilers’
operators.

As an integrated CHIMEC’s policy,

this document will introduce the operators
to a list of:
⇒ Problems found
⇒ Possible Causes
⇒ Suggested Solutions to problems
that may be common in boilers’
operational conditions9.

The Tables below (9-1 to 9-3),

provide common Troubleshooting Tips for
the following steps:
⇒ Water Pre-Treatments
⇒ Boiler’s Internal Water
⇒ Condensate Circuit
Once again, the information here in
reported, should always be supported by
the experience of the operators.

9
The list is definitively not exhaustive.

CHIMEC S.p.A. Water Technology Unit - BOILER’S OPERATORS’ HANDBOOK - 40

Table 9-1: Water Pre-Treatments Trobleshooting.

What Is the Problem? Possible Causes Suggested Problem’s Solution

Check/Verify Cationic Resin

High pH Water Sodium entrainment
Efficiency and conditions

Check/Verify Anionic Resin

Low pH Water Silicic Acid entrainment
Efficiency and conditions

ƒ Incorrect Regeneration ƒ Check/Verify Procedure

System
ƒ Resins Fouled ƒ Check/Verify Correct Cleaning
Short Running Time
ƒ Resins Damaged ƒ Replace Resins
ƒ Check/verify Hot Steam
ƒ System Low Temperature
Feedrate
ƒ Low Retention Time
O2 found after deaerator ƒ Check/Verify System’s Streams
ƒ Low O2 Scavenger
ƒ Adjust System’s Venting/Adjust
Dosage
product(s) dosage

Table 9-2: Boilers’ Internal Water Troubleshooting.

What Is the Problem? Possible Causes Suggested Problem’s Solution

High Conductivity Low Blowdown Increase blowdown

ƒ Acidic Hydrolysis Salts ƒ Check/Verify Demineralization

Unit correct performance
ƒ High Blowdown
Low pH Water
ƒ Low Alkalizing product(s) ƒ Lower Blowdown
Dosage ƒ Increase product(s) dosage
ƒ Low Blowdown
ƒ Increase Blowdown
High pH Water ƒ High Alkalizing product(s)
ƒ Lower product(s) dosage
Dosage

CHIMEC S.p.A. Water Technology Unit - BOILER’S OPERATORS’ HANDBOOK - 41

Table 9-3: Condensate Circuit Troubleshooting.

What Is the Problem? Possible Causes Suggested Problem’s Solution

ƒ Low Alkalizing product(s) ƒ Increase product(s) dosage
Dosage
ƒ Check/Verify system losses and
Low pH Water ƒ Air Intakes seals
ƒ Low Alkalizing product(s)
ƒ Increase product(s) dosage
Dosage

ƒ Process induced Pollution ƒ Check/Verify system losses and

Iron found in the seals
Condensate System ƒ Low pH ƒ Increase Alkalizing product(s)
Dosage

CHIMEC S.p.A. Water Technology Unit - BOILER’S OPERATORS’ HANDBOOK - 42

10 Tests’ Answers

1.1 Universal solvent

1.2 Surface, groundwater
1.3 Suspended, dissolved, dissolved
1.4 µS / cm
1.5 pH
1.6 Acid, basic

2.1 Acids
2.2 Anionic
2.3 Decreases, Increases
2.4 Strong/weak acids, strong/weak bases
2.5 Strong

3.1 Oxygen, Carbon Dioxide, Ammonia

3.2 Partial Pressure
3.3 Lower
3.4 Readily Available, Does not pollute water and warms up water
3.5 Suspended
3.6 Chemical Oxygen Scavengers, Sodium Sulphite, DEHA, Ascorbic and Erithorbic Acid.

4.1 Firetube
4.2 Watertube
4.3 Convection, Radiation
4.4 Downward, Lower Cylindrical Body, Upward, Upper Cylindrical Body, Natural
4.5 Superheater
4.6 Blowdown
4.7 Lower
4.8 Feedwater and Blowdown
4.9 Lower

5.1 Deposition
5.2 Velocity/Steep
5.3 Steam/Water phase
5.4 Precipitating, Dispersing
5.5 Chelates Based
5.6 Precipitating
5.7 Precipitating, Dispersing
5.8 Incoherent, Blowdown

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6.1 Steam Quality
6.2 Carryover
6.3 Design, separation, high, working
6.4 Main
6.5 Foaming
6.6 Attemperating

7.1 Oxygen and Carbon Dioxide

7.2 Bicarbonates
7.3 Condenser, Deaerator
7.4 Amines, Neutralizing, Filming, Scavengers
7.5 Neutralizing, Basicity, Distribution
7.6 Blends
7.7 Steam Header

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