Water Treatment Handbook

UNITOR
ASA
Mail: P.O. Box 300 Skyen, N-0212 Oslo, Norway

Office: Drammensvn. 211, N-0277 Oslo, Norway
Tel: +47 22 13 14 15. Fax: +47 22 13 45 00
Tlx: 76004 UNTOR N
ID. NO. 08 173 REV. NO. 00 LOBO 09.97 5K COUNTRY OF ORIIGIN: NORWAY
Water
Treatment
Handbook
C H E M I C A L S
Marine Chemicals
Water Treatment
Handbook
A PRACTICAL APPLICATION MANUAL
1st Edition
Unitor ASA, P.O. Box 300 Skyen, N-0212 Oslo, Norway

Office: Drammensveien 211, N-0277 Oslo, Norway
Tel: +47 22 13 14 15. Fax: +47 22 13 45 00
Tlx: 76004 UNTOR N
ID. NO. 08 173
REV. NO. 00
LOBO
09.97
5K
COUNTRY OF ORIGIN: NORWAY
FOREWORD
This manual has been edited to specifically apply to Unitors Marine Chemical
Market. It has been prepared to give the marine engineer basic insight into
the chemical water treatment of marine propulsion boilers, low pressure
auxiliary and exhaust boilers, diesel engines, evaporators and other
associated equipment.
The purpose and design of Unitor marine chemical products is to provide
the marine engineer with the most environmentally-friendly products and with
the most practical and simple applications of their use.
Unitor has designed the Spectrapak test kits to accurately determine
chemical concentrations of the various products and systems they are being
used to check. The Spectrapak tablet system is the most practical and
economical testing system available to the marine engineer. Our water
treatment programmes are designed to utilize the simplest water testing
procedures along with the assistance of our worldwide service personnel and
Unitors Laboratories which provide the technical expertise required to
answer all questions in regard to marine chemical applications.
Unitors products have been designed to provide the ship operator with
a variety of products and systems to cover all requirements for the many
different types of boiler systems and crew requirements, which will be
detailed in this manual.
Unitor has introduced the most up-to-date log review system to utilize
todays technology in communications and computers to provide the operator
and marine engineer with a Rapid Response to our log review system.
Unitor is dedicated to providing the marine operator with the most reliable
products available in the marine chemical industry along with the many other
areas of expertise and standardisation worldwide. Our products and services
are available 7 days a week and we are committed to maintaining this for the
marine industry.
INDEX
Page
INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV
1 Water Treatment Philosophy and Overview . . . . . . . . . . . . . . . . . . . . . . .
2 Basic Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3 Problems of Boiler Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

4 Types of Boiler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5 Boiler Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
6 Unitor Boiler Water Treatment Products . . . . . . . . . . . . . . . . . . . . . . . . . 28
7 Combined Treatment for Low Pressure Boiler Water . . . . . . . . . . . . . . . 29
8 Tests for Boiler Water, Low Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
9 Unitor Coordinated Treatment Products . . . . . . . . . . . . . . . . . . . . . . . . . . 34
10 Tests for Boiler Water, Medium Pressure . . . . . . . . . . . . . . . . . . . . . . . . 38
11 High Pressure Boiler Water Control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
12 Boiler Wet Layup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
13 Boiler Blowdown . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
14 Chemical Cleaning of Boilers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
15 Diesel Engine Cooling Water Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . 60
16 Reporting Analysis Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
17 Water Tests, Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
18 Evaporator Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
19 Marine Equipment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
20 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
II
WATER TREATMENT HANDBOOK
III
INTRODUCTION
This Product Applications Handbook has been designed to provide specific
information on the variety of chemical and related products and systems
available from Unitor.
This handbook will give all the information required to maintain these various products, including the application of individual chemical products to
properly maintain Low Pressure, Medium Pressure and High Pressure Boilers,
Diesel Engine Cooling Systems and Evaporators.
Single Function Treatment Products:
1. Hardness Control
2. Alkalinity Control
3. Oxygen Control (Hydrazine)
4. Catalysed Sodium Sulphite (Powdered & Liquid)
5. Condensate Control
6. Boiler Coagulant
Low Pressure Boilers, Water Treatments:
1. Combitreat (powdered)
2. Liquitreat
1 Water Treatment Philosophy

and Overview
1.1
TYPES OF WATER
General
Water could generally be described as the most important of all chemical
substances. Its chemical designation is H2O; the water molecule is composed
of 2 Hydrogen atoms and 1 Oxygen atom.
Natural water
Raw water is the description of the water to which we have daily access.
We can obtain our water from:
1. The ocean
2. Surface sources (e.g. from lakes)
3. Underground sources
The water will vary in composition.
The natural water cycle may be as below:
Cooling Water Treatments:

1. Dieselguard NB (powder)
2. Rocor NB Liquid
Sea Water Cooling Treatment:
1. Bioguard
Evaporator Treatment:
1. Vaptreat
While it is evaporating from the surface of a lake or the ocean into the atmosphere, we can designate the water vapour H2O. In the atmosphere, clouds
will form, and during suitable humidity and temperature, the clouds will
deposit water (rain). While the rain is falling towards the earth, it absorbs
gases which are in the air, e.g. CO2 (Carbon Dioxide), SO2 (Sulphur Dioxide)
and O2 (Oxygen).
When the water hits the earth, it absorbs additional Carbon Dioxide (from
biological degradation). The rainwater which is now slightly acid will dissolve
various minerals from the soil.
IV
2 Basic Chemistry
The chemistry of water
It is necessary to examine some of the basic theories in order to understand
the various problems associated with water treatment.
While rain is falling through the air, it absorbs gaseous contaminants, e.g.
O2 (Oxygen), which solubility in pure water depends on temperature.
At 20 C, 9 mg/l O2 may dissolve, and
at 50 C approx. 5.5 mg O2/l,
TEMPORARY HARDNESS (Alkaline Hardness) is due to bicarbonates of

Calcium and Magnesium which are Alkaline in nature. They are temporary
because when heated they rapidly break down to form Carbon Dioxide and
the corresponding carbonates which deposit as scale.
PERMANENT HARDNESS (Non-Alkaline Hardness) is due mainly to
Sulphates and Chlorides of Calcium and Magnesium which are acid in nature.
They are permanent and do not break down, but under certain conditions
deposit to form scale of varying hardnesses.
and at 90 C approx. 1.5 mg O2/l, and
2.1
at 100 C approx. 0.0. mg O2/l,

so, the higher the temperature, the less O2 can dissolve in water.
CO2 (Carbon Dioxide) dissolves in water as follows:
CO2 + H2O > H2CO3
H2CO3 is a very weak acid. In contact with CaCO3 (ordinary lime), it is reactive
and the lime dissolves as follows:
CaCO + H CO > Ca++ + 2HCO
3
Ca(HCO3)2 is called Calcium Bicarbonate.

SO2 (Sulphur Dioxide) is an air pollutant which stems from flue gases, so there
is usually a high atmospheric content of this gas around industrial areas.
2SO2 + O2 + 2H2O > 2H2SO4
H2SO4 is called Sulphuric Acid, and this acid also dissolves lime (CaCO3)
as follows:
CaCO3 + H2SO4 > CaSO4 + H2O + CO2.
CaSO4 is called Calcium Sulphate (gypsum).
In other words, the gases dissolved in the water will increase the leaching of
the subsoils minerals, so that we may have solutions in water due to:
TOTAL HARDNESS
2 / BASIC CHEMISTRY
Temporary hardness
Permanent hardness
Calcium Bicarbonate
Ca (HCO3)2
Magnesium Bicarbonate
Mg (HCO3)2
Calcium Sulphate
CaSO4
Magnesium Chloride
MgCl2
BOILER WATER TREATMENT FUNDAMENTALS
The concept of employing water, fresh or distilled, as a power generating

source and heat exchange medium originated and was realised with the
inception of the steam generator or boiler, and has been applied most
successfully and beneficially in this manner ever since.
Water has the ability to transfer heat from one surface to another, thereby
maintaining the system within the correct operational temperature range
while generating steam to carry out work. However, water can adversely
affect metal components under the operational conditions normally found in
steam boilers and other heat exchange devices. The extent of deterioration
depends on the specific characteristics of the water and the system in which
it is being used.
In order to counteract the detrimental properties normally attributed to
water and its contaminants (dissolved and suspended solids and dissolved
gases), special chemical treatment programmes have been devised.
Accepted water treatment processes and procedures are constantly being
upgraded and modernised, and new methods are being developed to
complement and/or replace older ones. Unitor utilizes the most modern,
practical programmes for the marine operator.
Although water from marine evaporators and boiler condensate return
systems is essentially pure, minute quantities of potentially harmful
salts and minerals can be carried by this composition and feedwater into
the boiler, where they will accrue, ultimately resulting in serious problems in
the steam generating unit. In addition, the water can also contain dissolved
gases, i.e. CO2 and Oxygen, which can result in corrosion of the system.
Using unprocessed fresh water (e.g. shore water) as a makeup source can
present some of the same problems experienced with distilled water, but in
addition, certain contaminants which are naturally present in fresh water can
be extremely destructive in boiler systems if not dealt with promptly and effectively. Soluble salts such as Chloride, Sulphate and Carbonate are present
as electrolytes in the untreated water, leading to galvanic and other types of

corrosion, depending on the conditions in the system. In addition, Sulphates
and Carbonates have the potential to form insoluble, adherent, insulating
hard water scale deposits on heat exchanger surfaces.
2.2
CONTRIBUTING ELEMENTS
WHICH AFFECT BOILER WATER TREATMENT
Most dissolved mineral impurities in water are present in the form of ions.
These ions contain an electrical charge which is either positive (cation) or
negative (anion). These ions can join together to form chemical compounds.
To know which ions will combine, we need to know their electrical charge.
Ions of concern to us include the following:
Positive
ions
Chemical
symbol
Negative
ions
Chemical
symbol
Sodium
Calcium
Magnesium
Hydrogen
Na+
Ca++
Mg++
H+
Chloride
Bicarbonate
Carbonate
Hydroxide
Cl
HCO3
CO3
OH
Cations will combine only with anions.

An example of this combining of ions is the action between Calcium and
Carbonate. The chemical compound which forms is Calcium Carbonate.
Other impurities which will affect the boiler water treatment control
include Copper, Iron Oxides, oil and dissolved gases.
2.2.1 Copper
Copper is introduced into a system by corrosion of Copper piping and
Copper alloys. In boilers, the source of this corrosion could be dissolved
gases in the boiler water or the excessive use of Hydrazine which will
corrode Copper and Copper alloys, allowing Copper to be carried back
to the boiler.
Copper in the boiler displaces metal from the tube surfaces and
plates out on the tubes. This condition often occurs under existing scale
and sludge deposits, which is known as under deposit Copper corrosion. Copper deposits are a serious problem in high pressure boilers.
Waterside deposits may be submitted to Unitor for complete analysis
and determination of the correct procedures to follow for cleaning.
2.2.2 Oil
To prevent oil from entering condensate and feedwater systems, certain
safety equipment is generally incorporated to detect, remove, and
arrest such contamination.
2 / BASIC CHEMISTRY
Oil contamination may occur through mechanical failure, for

example, faulty oil deflectors at turbine glands passing lubrication oil to
gland seal condensers and main condensers, etc., or undetected leaks
at tank heating coils.
Any oil film on internal heating surfaces is dangerous, drastically
impairing heat transfer. Oil films therefore cause overheating of tube
metal, resulting in possible tube blistering and failure.
If oil contamination is suspected, immediate action must be undertaken for its removal.
The first corrective measure in cleaning up oil leakage is to find and
stop the point of oil ingress into the system. Then, by using a Unitor
degreaser, a cleaning solution can be circulated throughout the boiler
system to remove the existing oil contamination. Complete details on
this cleaning operation are covered later in the handbook.
Boiler Coagulant can assist in removing trace amounts of oil
contamination. Consult your Unitor representative for more specific
recommendations.
2.2.3 Iron Oxides
Iron may enter the boiler as a result of corrosion in the pre-boiler
section or may be redeposited as a result of corrosion in the boiler or
condensate system. Often, Iron Oxide will be deposited and retard heat
transfer within a boiler tube, at times resulting in tube failure. This
usually occurs in high heat transfer areas, i.e. screening tubes nearest
to the flame.
When iron is not present in the raw feedwater, its presence in the
boiler indicates active corrosion within the boiler system itself.
Rust, the reddish form, is fully oxidized. More often, in a boiler with
limited Oxygen, it is in the reduced or black form as Magnetite (Fe3O4).
Fe3O4 is magnetic and can be readily detected with a magnet. It is
a passivated form of corrosion and its presence shows that proper
control of the system is being maintained.
2.2.4 Magnesium Carbonate (MgCO3)
Magnesium hardness in fresh water usually accounts for about onethird of the total hardness. The remaining two thirds can normally be
attributed to calcium.
Since Magnesium Carbonate is appreciably more soluble in water
than Calcium Carbonate, it is seldom a major component in scale
deposits. This is due to the preferential precipitation of the Carbonate
ion by Calcium as opposed to Magnesium which remains in solution
until all soluble Calcium is exhausted.
Once this point is reached, any free Carbonate remaining in solution
will combine with the Magnesium and begin precipitating out as
Magnesium Carbonate when the solubility of this salt is exceeded.

Because of this latter phenomenon, where soft water is used for
boiler structure, any Magnesium present must be removed along with
the Calcium.
2.2.5 Magnesium Sulphate (MgSO4)
Magnesium Sulphate is an extremely soluble salt, having a solubility of
20 % in cold water and 42 % in boiling water. It exists as the Sulphate
only in water with a low pH. Because of its high solubility, it will not
normally precipitate. The Sulphate ion, however, will be precipitated by
the Calcium hardness present if no free Carbonate exists.
2.2.6 Magnesium Chloride (MgCl2)
Magnesium Chloride, like Magnesium Sulphate, is soluble in fresh water.
In the high temperature and alkaline conditions normally maintained in a
boiler, any soluble Magnesium ions in the boiler water become extremely
reactive with Hydroxyl ions, which may be present in high concentrations
in this type of environment.
This can result in the formation of Magnesium Hydroxide precipitates which form insulating scale on the boiler tube surfaces. If Chloride
ions are also available, they react with the Hydrogen ions previously
associated with the precipitated Hydroxyl ions, to form Hydrochloric
acid, thereby lowering the alkalinity of the water. If this situation is
allowed to continue, the pH of the boiler water will decrease until acid
conditions result in corrosion of the metal surfaces. Unlike Carbonate
and Sulphate ions, the Chloride ion does not precipitate in the presence
of soluble Calcium.
2.2.7 Silica (SiO2)
Silica scale is not normally found in boiler systems except in minute
quantities. It can be admitted to the system when severe carryover
occurs in evaporators processing water with a high Silica content.
Other sources of such feedwater may be high Silica river or raw fresh
water as well as distilled/deionized or unprocessed fresh water
which has been stored and taken from cement-washed or silicatecoated tanks.
Once formed, pure Silica scale is extremely difficult to remove. It
forms a tight adherent glass-like film on metal surfaces, thereby preventing proper heat transfer. In addition, in steam-generating devices it
can carry over with the steam coating the after-boiler sections, particularly the superheater.
If a turbine forms part of the system, the Silica can deposit on the
blades as well as cause erosion of the finned surfaces of the blading,
resulting in imbalance of the turbine, which in turn may result in
turbine failure.
10
2 / BASIC CHEMISTRY
Besides the pure form of Silica (i.e. Silicon Dioxide), possible Silicate
deposits can form in combination with Calcium and Magnesium, which
are extremely insoluble in water and very difficult to dissolve and
remove.
Besides being an extremely difficult process, the chemical removal
of Silica and silicate deposits can also be very hazardous, since it
involves the use of Hydrofluoric Acid or Ammonium Bifluoride, both of
which are severely destructive to human tissue by inhalation, ingestion
and physical contact. In some instances, alternate acid and alkaline
washings have been used to successfully combat this problem.
The only alternative to chemical cleaning is mechanical removal.
2.2.8 Calcium Carbonate (CaCO3)
Calcium Bicarbonate alkalinity exists in almost all unprocessed fresh
water under normal conditions. Its solubility is about 300400 ppm
at 25 C. If heat is applied or a sharp increase in pH occurs, the Calcium
Bicarbonate breaks down to form Carbon Dioxide and Calcium
Carbonate.
While the bicarbonate salt has been shown to be moderately soluble in
water, the solubility of Calcium Carbonate at 25 C is only about 14 ppm.
This value continues to decrease as the temperature increases, becoming the least where the temperature is greatest. In a boiler, this would be
on the surface of the furnace tubes where contact is made with the
water. The resulting insoluble Calcium Carbonate precipitate forms
building block-like crystals which adhere not only to one another, but
also to the hot metal surfaces, resulting in a continuous, insulating
scale deposit over the entire heat exchange area.This deposit will continue to grow, building upon itself to form a thick coating until all the
Calcium Carbonate produced is exhausted. If suspended matter is also
present in the water, it can become entrained within the crystal
structure, creating a larger volume of deposit than that formed by the
Carbonate precipitation alone.
If this condition is allowed to continue, heat exchange efficiency
at the water/tube interface falls rapidly, resulting in an increase in fuel
consumption necessary to compensate for the decline in thermal
transfer and to regain design temperature as well as steam production
requirements. This increase in the furnace-side temperature needed
to run the system at optimum conditions exposes the metal surfaces
to overheating which, in turn, can cause blistering fatigue, fracture,
and failure of boiler tubes. In addition, if pockets of water become
trapped beneath the scale deposits and are in contact with the hot
metal surfaces, concentration of acid or alkaline materials may
occur and lead to the formation of local electrolytic cells (underdeposit corrosion).
11
2.2.9 Calcium Sulphate (CaSO4)

Although Calcium Sulphate is more soluble in water than Calcium
Carbonate, it can be just as troublesome when present in boiler and
cooling water systems. Calcium Sulphate, like Calcium Carbonate, but
unlike most salts, has an inverse temperature/solubility relationship in
water. As gypsum, the hydrated form in which Calcium Sulphate is normally present in fresh water, its solubility increases until a temperature
of about 40 C is achieved. At 40 C, its solubility is 1,551 ppm; at 100 C,
which is the normal boiling point of water, its solubility decreases to
1,246 ppm, and at 220 C it falls to 40 ppm. Calcium Sulphate reacts at
high-temperature surfaces essentially in the same manner as Calcium
Carbonate and with the same effects and consequences. However,
whereas Calcium Carbonate deposits are relatively easy to remove
using a comprehensive acid cleaning procedure, Calcium Sulphate is
essentially impervious to the effects of normal acid descaling methods
and usually must be removed by mechanical means.
D. ALKALINITY RELATIONSHIP TABLE
2.2.10 Dissolved Gases

Gases such as Oxygen and Carbon Dioxide that are dissolved in distilled
or fresh water, will further contribute to the deterioration of the boiler
system. Dependent upon conditions in the system (e.g. temperature,
pressure and materials of construction), dissolved Oxygen can cause
pitting corrosion of steel surfaces, while Carbon Dioxide lowers the pH,
leading to acid and galvanic corrosion. Carbon Dioxide has the added
disadvantage of forming insoluble carbonate scale deposits in an alkaline environment when Calcium and Magnesium are present.
*This is the correct alkalinity relationship for boiler water
2.2.11 Acidity, Neutrality and Alkalinity

All water can be classified into one of these categories. Acidity,
Neutrality and Alkalinity are only very general terms. We require more
accurate methods of testing to know the degree of each condition.
When testing boiler water, it is important to understand what you are
testing for.
Hydroxide
Alkalinity
Carbonate
Alkalinity
Bicarbonate
Alkalinity
P Alkalinity
=0
Equal to
total
P Alkalinity
less than
1/2 M Alkalinity
2 times
P Alkalinity
M Alkalinity
minus 2 times
P Alkalinity
P Alkalinity
equal to
1/2 M Alkalinity
2 times
P Alkalinity
*P Alkalinity
greater than
1/2 M Alkalinity
2 times
P Alkalinity
minus
M Alkalinity
2 times the
difference
between M
and P Alkalinity
P Alkalinity
equal to
M Alkalinity
Equal to
M Alkalinity
pH
The pH of a solution is a measurement of the concentration of active acid or
base (alkaline constituent) in a solution.
To give a precise definition, pH is the negative logarithm of the Hydrogen
ion concentration.
A simpler explanation of pH is that it is a measure of relative acidity or alkalinity of water. In other words, it reflects how acidic or alkaline the water is.
pH is the number between 0 and 14 which denotes the degree of acidity
or alkalinity.
A pH value of 7 indicates neutral. Below 7 indicates increasing acidity.
Above 7 up to 14 indicates increasing alkalinity.
Acidic
Neutral
Alkaline
A. ALKALINITY. The presence of Alkalinity in a water sample may be

due to many different substances. For the sake of simplicity, the
presence of Bicarbonate, Carbonate and Hydroxide contributes to the
alkalinity of water.
B. P ALKALINITY. Phenolphtalein (P) Alkalinity (pH values greater than

8.3) measures all the Hydroxide and one half of the Carbonate Alkalinity
which is sufficient for our purpose of control. Bicarbonates do not show
in this test as they have a pH of less than 8.4.
pH is a very important factor for determining whether a water has a corrosive

or scale-forming tendency.
Water with a low pH will give rise to corrosion of equipment.
10
11
12
13
14
C. M ALKALINITY. Total Alkalinity or M Alkalinity (pH values greater

than 4.3) measures the sum of Bicarbonate, Carbonate and Hydroxide
Alkalinity.
12
2 / BASIC CHEMISTRY
13
3 Problems of Boiler Water

Feedwater produced by distillation for use in a boiler is not pure, even with a
good distillation method. Worse still is ordinary water taken from ashore to be
used as feedwater. The water will contain some of the elements (impurities)
mentioned in Chapter 5.
Problems will then arise when the water is used in the boiler. The types
of problem will depend on the type of impurities and in which quantities they
are present.
3.1.1 Pitting Corrosion

Pitting is the most serious form of waterside corrosion and is the
result of the formation of irregular pits in the metal surface as shown in
the figure below. Evidence of pitting is usually found in the boiler shell
around the water level and is most likely caused by poor storage procedures when the boiler is shut down for lengthy periods, and by inadequate Oxygen scavenging.
The most common problems are:

CORROSION
SCALING
CARRYOVER
3.1
CORROSION
The corrosion processes can affect boilers in the following ways:

General wastage is the overall reduction of metal thickness and is common
in heating surface areas, such as boiler tube walls. This thinning of boiler
tubes is often found in boilers having open feed systems (mostly auxiliary
boilers) without any protective treatment. An example of wastage is given in
the figure below.
General wastage of a boiler tube.
14
3 / PROBLEMS OF BOILER WATER
Pitting corrosion.
3.1.2 Stress Corrosion

Stress corrosion cracking is the process caused by the combined
action of heavy stress and a corrosive environment. The stages of failure of the metal due to stress corrosion are shown below. Corrosion is
initiated by breakdown of the surface film followed by the formation of a
corrosion pit which becomes the site for stress corrosion cracking,
eventually leading to mechanical failure due to overloading of the
mechanical strength of the metal. This form of attack is often found
around the ogee ring in vertical auxiliary boilers, when undue stressing
is set up by poor steam-raising procedures.
Stress corrosion
15
3.1.3 Other Related Problems

Corrosion fatigue occurs when a sufficiently high alternative stress
level causes failure of the subjected material. It is the joint action of a
corrosive environment and cyclic stressing and results in a series of
fine cracks in the metal. This is found in water tube boilers where irregular circulation through tubes in high temperature zones induce these
cycling stresses.
Caustic cracking results from the contact of water of concentrated caustic alkalinity and steel which has not been stress relieved,
e.g. in riveted seams. This form of cracking follows the grain boundaries. This is rarely observed nowadays, as both high and low pressure
boilers are usually of all welded construction and are stress relieved.
Caustic corrosion takes place only in high pressure boilers (above
60 bar) when excessively high concentrations of Sodium Hydroxide
(Caustic Soda) cause breakdown of the magnetite layer and localised
corrosion. This form of attack is often controlled by the coordinated PO4
Treatment Programme.
Hydrogen attack is another form of corrosion damage that can
take place in ultra high pressure boilers.
Whichever form of corrosive attack occurs, the risk of tube failure or
serious structural damage is very apparent, both often leading to considerable expense in the shape of repair costs.
3.2
SCALING
Causes and Effects

If the inside of a boiler is scaled, there is a great risk that the boiler material
will overheat, leading to tube failure. The efficiency of operation will also be
adversely affected.
Hardness in the feedwater will usually present problems in relation to the
operation of boilers. Hardness of more than 5dH (90 ppm as CaCO3) in the
feedwater will, as the temperature rises, cause an increase in the formation
of sludge in the feedwater tank. If scale-preventing chemicals are put into the
feedwater tank, this problem will be aggravated, as nearly all precipitation of
sludge will take place in the feedwater tank. The suction pipe stub of the feed
water line will usually be placed 510 cm above the bottom. However, if the
feed water is not very clean, sludge will after a time be sucked into the piping
and choking may occur. In a modern centrifugal pump, the very narrow vanes
may be blocked, which will cause the pump to stop. Finally, there is a risk of
the valves sticking and becoming blocked.
In spite of the fact that a boiler plant may be equipped with a water
treatment system of some sort, there will always be a risk of hardness or
other type of pollution in the feedwater, because:
1. The capacity of the water treatment system is insufficient.
2. There are defects in the water treatment system.
3.1.4 Factors Affecting Corrosion
16
1) pH
Metal oxides are more soluble as pH

decreases. Corrosion is increased.
2) Dissolved solids
Chloride and Sulphate can penetrate

passive metal oxide film which protects the
base metal from corrosion.
3) Dissolved gases
Carbon Dioxide and H2S reduces pH and

promotes acid attack. Oxygen promotes
pitting corrosion.
4) Suspended solids
Mud, sand, clay, etc. settle to form deposits,

promoting different corrosion cells.
5) Micro organisms
Promote different corrosion cells.
6) Temperature
High temperature increases corrosion.
7) Velocity
High velocity promotes erosion/cavitation.
8) Copper
Copper ions plate out on steel surfaces

and promote pitting corrosion.
3. The condensate is polluted:

a. By heat exchanger leaks
b. By lubrication oil
Daily analysis of the quality of the feedwater will ensure that action can be
taken in time to prevent irregularities.
Hardness in the boiler water will inevitably lead to the formation of scale
and the rate of this formation will depend on the composition and quantity of
the hardness, on the temperature conditions in the boiler and on the circulation in the boiler.
Increased surface heating effect means increased production of steam
bubbles, which again will make more boiler water pass the spot on the
heating surface (where the steam bubbles are formed) and this spot will thus
also be passed by the hardness-producing and corroding salts in the boiler
water. In addition, the most common hardness salts are less soluble at
increasing temperatures.
This explains why the largest amount of encrustation will always be found
where the temperature of the heating surface is the highest.
Scale formed just at this point means that the critical temperature of the
boiler material will be reached quickly and that damage to the boiler will be
inevitable.
17
3.3
Illustration of
Typical Conditions With
a Clean Boiler Tube
Change in Conditions When

a Layer of Scale of just 3 mm
Thickness Exists
CARRYOVER
Carryover is any contaminant that leaves the boiler with the steam.
Carryover can be:
Solid
Liquid
Vapour
Effects of carryover:
Deposits in non-return valve
Deposits in control valves
Deposits in superheaters
Deposits on turbine
Carryover in superheaters can promote failure due to overheating.

Turbines are prone to damage by carryover, as solid particles in steam can
erode turbine parts. When large slugs of water carry over with steam, the
thermal and mechanical shock can cause severe damage.
The scale causes the fuel consumption to increase by approx. 18 percent.

Stress will arise in the steel as a result of the insulating effect of the scale.
Excess Fuel Consumption in %,

depending on Thickness of Scale
Causes of carryover:
Mechanical:
Priming
Soot blowing
Sudden load changes

High water level
Chemical:
Foaming due to:
High Chlorides
Suspended solids
High TDS
Oil
Boiler design
High alkalinity
Silica
Curve of middle values. The differences in the test results can be

explained by differences in the composition of scale (poroushard).
The most common form of encrustation in a steam system stems from

carryover. The boiler manufacturers stipulate a maximum allowed salinity of
the boiler water (as a rule at 0.4 Be = 4000 mg salts dissolved per litre). If this
value is exceeded, there is a risk of normal bubble size being prevented;
larger bubbles will be produced and the turbulence in the water surface will
increase and cause foaming. The foam may be carried over with the steam,
particularly when the generation of steam is at maximum, which causes boiler
water (containing Sodium Hydroxide and salt) to pass out into the steam
pipes.
The content of Silicic Acid is important for boilers with high pressures.
Silicic Acid in its volatile form may be carried away with the steam and be
deposited on turbine blades, for instance, on which it will form a very hard,
porcelaine-like scale.
However, not only the chemical composition may cause carryover. Circumstances such as periodic overloads, periods of a too high a water level (or more
correctly: too small a steam volume) are two of the most common causes.
Finally, impurities from the condensate, such as oil from the preheaters
coils if they are leaking are very common causes of priming.
18
19
4 Types of Boiler
What is a boiler?
A boiler is a steel pressure vessel in which water under pressure is converted into steam by the application of combustion. In other words, it is
simply a heat exchanger which uses radiant heat and hot flue gases, liberated
from burning fuel, to generate steam and hot water for heating and
processing loads.
There are two types: Fire tube boilers and water tube boilers.
4.1
FIRE TUBE BOILER
Hot flue gases flow inside tubes that are submerged in water within a shell.
Pressures up to about 10 bar
Produce up to 14 tonnes of steam/hr
Can meet wide and sudden load fluctuations because
of large water volumes
Usually rated in HP
4.2
WATER TUBE BOILER
Typical packaged boiler. Packaged boilers include a pressure vessel, burner, all the controls, air
fans, and insulation. The boiler is tested at the manufacturers plant and shipped to the customer,
ready for use, when the fuel lines and piping and electrical connections have been installed.
Water flows through tubes that are surrounded by hot combustion gases
in a shell.
Usually rated in tons of steam/hr
Used for H.P. steam
High capacity
BOILERS HAVE SIX BASIC PARTS
1)
2)
3)
4)
5)
6)
Burner
Combustion space
Convection section
Stack
Air fans
Controls and accessories
Typical Scotch Marine firetube boiler (courtesy of Orr & Sembower, Inc.).
20
4 / TYPES OF BOILER
21
4.3
FIRETUBE BOILERS
Wet back designs

Have a water wall at the back of the boiler in the area where combustion
gases reverse direction to enter tubes.
Dry back designs
Refractory is used at the back, instead of a water wall. Internal maintenance
is simplified, but refractory replacement is expensive and overheating,
gauging and cracking of tube ends at the entrance to return gas passages
often cause problems.
4.5
HIGH TEMPERATURE WATER (HTW) HEATING SYSTEMS
In recent years, interest has been revived in high temperature hot water
heating systems for institutional, industrial and commercial plants. By
increasing the temperature and pressure of the hot water and increasing the
size of the generators, some advantages are gained over the low pressure
steam heating systems previously used. In other cases, special forced
circulation boilers have been designed, which consist of many rows of tubes
without a steam drum. In another type, heat is supplied by steam from
a standard type of boiler which heats the water in a direct contact heater.
This is referred to as a cascade system.
WATERSYSTEM AND STEAMSYSTEM
4.4
CLAYTON STEAM GENERATOR
The coil type generator is a vertical coil with fuel combustion taking place
inside the coil. High quality feedwater and a closely monitored chemical treatment programme are mandatory. The most common problem is Oxygen
pitting on the inside portion of the coil near the fire. The two most common
name brands are Vapor-Clarkson and Clayton.
22
4 / TYPES OF BOILER
Medium-sized watertube boilers may be classified according to three basic tube arrangements.
23
5 Boiler Systems
4.6
FIRETUBE BOILERS
Advantages:
Lower initial cost
Few controls
Simple operation
Disadvantages:
Drums exposed to heat, increasing the risk of explosion
Large water volume, resulting in poor circulation
Limited steam pressure and evaporation
WATERTUBE BOILERS
Advantages:
Rapid heat transmission
Fast reaction to steam demand
High efficiency
Safer than firetube boilers
5.1
TYPICAL BOILER SETUP ON A MOTOR SHIP

5.1.1 The Boiler System
This does not just consist of a boiler. As indicated by the figure above, it
is a complete plant. Most motor ship boilers operate at low pressure,
that is, not more than 20 bar pressure. This makes it suitable for the
single treatment: the combined boiler water treatment.
The steam plant consists of the following:
Disadvantages:
More control than firetube boilers
Higher initial cost
More complicated to operate
Storage tank
This tank will hold the make-up water to be supplied to the various
systems as they lose water through leaks and through evaporation.
Normally, this water is made by a low pressure evaporator (this will
be described later on). The water produced in this way is normally of
good quality if the evaporator is set up correctly. When it is introduced
to the boiler, it will require the minimum amount of treatment. However,
at some stage the vessel will very likely take water from ashore, and
the quality can vary considerably. This water would probably require
more treatment to correctly condition it for use.
Hot well, observation tank or cascade tank
This has a very important function for the dosing of chemical treatments. This is where all the water collects on returning from the various
areas where steam has been used. It is also where water enters the
system from the storage tank(s) to make up the quantity required in the
system. If the steam has been used for heating fuel, the returns from
that tank may contain oil, or if cargo heating has been used, some of
24
4 / TYPES OF BOILER
25
the cargo product may be returned with the steam. That is why this tank
is sometimes called the observation tank steam returns can be
inspected for contamination here. There is a series of plates and filters
in the hot well which allows the contaminating oil, etc., to be removed.
Any sort of contamination is definitely not wanted in the water entering
the boiler, as it would cause damage. Dosage of the combined product
boiler water treatment is normally carried out into the hot well.
The system described provides the more common, modern system.

There are many systems where the exhaust gas boiler and the oil-fired
boiler are combined (composite boiler). A diagram of one is shown
below. One section of the tube is used for the oil-fired boiler and the
other section for the exhaust gases to pass through. This unit must be
situated in the funnel area because the exhaust trunking passes that
way and it is placed at a convenient point.
The boiler:
The water is drawn from the hot well by the feed pump and pumped into
the upper drum of the boiler (this is normally called the steam drum).
From here it circulates in the boiler, is heated and turns into steam.
There are normally two different ways in which it is heated.
5.1.2 The Steam Lines

The steam comes from the steam drum of the boiler and is distributed to
the areas where it is required. That is for heating tanks, fuel, hot water,
etc. No testing is required in this area under normal circumstances.
Once the useful heat has been taken out of the steam, it enters the
steam return lines and comes back to the drains cooler.
1. When the main diesel engine is running, the water is pumped

from the lower drum (called the water drum) and circulated through a
heat exchanger in the exhaust trunking which takes the exhaust gases
away from the engine to the atmosphere. The remaining heat in these
exhaust gases is used to generate the steam.
2. The auxiliary boiler has a burner (one or more) which uses either
heavy oil or diesel oil to provide the heat to produce steam. If the heat
available from the exhaust gases is insufficient, the oil fired burner(s)
can be used to make the steam required by the vessel.
5.1.3 Drains Cooler

This unit is another heat exchanger and it is there to ensure that all the
returning steam is turned to water. The returns would be a mixture of
hot water and steam before this cooler, and the cooler ensures that any
return steam is condensed to water.
The drains cooler normally uses sea water to cool the steam
returns, and this can be a source of contamination if there is a leak.
This will show up as a high chloride level in the feedwater if it occurs.
Sunrod Exhaust Gas Economiser.
26
5 / BOILER SYSTEMS
27
6 Unitor Boiler Water

Treatment Products
7 Combined Treatment for Low

Pressure Boiler Water
6.1
THE MAIN PURPOSE OF BOILER WATER TREATMENT IS
7.1
A. To eliminate the total hardness of the boiler water.
Liquitreat is a combined chemical treatment product suitable for use in small,

low pressure boilers. It precipitates hardness, provides the boiler water with
the necessary alkalinity, and scavenges dissolved Oxygen. Liquitreat should
be added when deemed necessary as shown by water analysis results.
If the boiler is open and not being fired, Liquitreat can be poured through
a manhole, but when the boiler is in operation, the treatment must be applied
through a special dosing line. When a dosing arrangement is utilized, the
chemical must be flushed to remove any residual left in the dosage lines and
equipment. If dosing lines are not fitted, the chemical can be added directly
to a feed tank as required. Ensure proper circulation through the feed tank
to allow the chemical to enter the boiler being treated. Under low load
conditions, complete changeover in the feed tank can take some time. It is
necessary to know the details of the flow pattern in the boiler for proper
testing and dosing of the chemical treatment to take place.
When several boilers have a common feed tank, dosing should be carried
out through independent dosing lines to ensure the proper treatment of each
boiler. Re-test within 2 hours of when the boiler water chemical treatment
was dosed to the boiler water.
For further recommendations on product dosage and control limits, refer
to the product data sheet in the Marine Chemicals Manual.
B. To maintain the correct pH and alkalinity values in feedwater and

boiler water.
C. To prevent corrosion, especially corrosion caused by Oxygen.
D. To prevent the formation of scale, among other things by
conditioning the sludge.
E. To avoid foaming.
6.2
UNITOR PRODUCTS
Combined Treatment
1. Liquitreat
2. Combitreat
Single Function Treatment
1. Alkalinity Control
LIQUITREAT
2. Hardness Control
7.2
3. Oxygen Control
Combitreat is a combined product chemical treatment similar to Liquitreat but

in powder form without Oxygen scavenger, which precipitates hardness and
provides the boiler water with the necessary alkalinity.
Combitreat should be applied as a solution and added when deemed
necessary as shown by water analysis results. The recommended dosage
must be dissolved in warm water, 3060 C in a suitable steel or plastic
container, not exceeding the solubility limit of 180 grams per litre. Combitreat
must be added slowly to the water (not vice versa) and the solution being
prepared must be constantly stirred.
Combitreat is best dosed by means of a bypass potfeeder directly in the
boiler water feed line. It can also be dosed into the hot well after premixing
with hot water at a ratio of 1 kg per 9 litres of water.
4. Catalysed Sodium Sulphite

5. Cat. Sulphite L
6. Boiler Coagulant
COMBITREAT
NOTE: In addition to our combined product chemicals, Condensate Control should be used in all boiler systems to
keep the Condensate pH level between 8.39.0. Also, the hot well temperature is of great importance when it comes
to Oxygen scavenging (ref. basic chemistry at the beginning of the book). We recommend that you maintain a hot
well temperature of between 70 C and 90 C. For further recommendations on product dosage and control limits,
refer to the product data sheet in the Marine Chemicals Manual.
28
6 / UNITOR BOILER WATER TREATMENT PRODUCTS
29
8 Tests for Boiler Water,

Low Pressure
8.1
UNITORS LOW PRESSURE COMBINED BOILER WATER

TREATMENT PROGRAMME
The tests recommended in order to maintain boiler water within the desired
level of quality when treating with Unitor Liquitreat/Combitreat are as follows:
A. P-Alkalinity Recommended Limits: 100300 ppm as CaCO3.
B. Chlorides 200 ppm maximum as Cl.
C. Condensate pH 8.39.0.
Dosage level of Liquitreat/Combitreat is based on the P-Alkalinity value of
the boiler water. However, Chlorides and condensate pH must also be
controlled and maintained as recommended. Knowledge of all relevant parameters is desirable to enable better interpretation and correct application
of treatment. To increase the condensate pH, use Unitors Condensate Control
in conjunction with your combined product boiler water treatment. It is
recommended that you dose Condensate Control on a continuous basis, to
maintain the condensate pH within the recommended range of 8.39.0
at all times.
8.2
CONTROLLING ALKALINITY
The alkalinity is a more accurate indicator of the boiler water condition than is
the pH. The Phenolphtalein (P) alkalinity is measured to determine whether
the correct conditions of alkalinity exist in the boiler to:
8.4
pH
Recommended limits of 9.511.0. An additional test to determine the pH of the

boiler water can be carried out to give a better overall understanding of the
boiler water quality. This test is optional.
The pH of the boiler water should be maintained within the range of
9.511.0 to prevent any corrosion attack on the boiler metal. pH values below
9.5 indicate, a greater possibility of corrosion and in such a situation,
treatment levels should be increased accordingly to restore boiler water
to optimum quality.
8.5
CONDENSATE pH
To control corrosion in after boiler, condensate and feedwater sections, the

condensate pH should be kept between 8.3 and 9.0. Monitoring the pH of this
water is very important in being able to maintain a complete Boiler Water
Treatment Management Programme.
8.6
TESTING REQUIREMENTS
8.6.1 Low Pressure Boiler Water Treatments:
A. Unitor Combined Treatment Products
a. Combitreat For systems up to 17.5 bar.
b. Liquitreat For systems up to 30 bar.
B. Test Equipment Unitor Spectrapak 310 Test Kit.
A. Provide a suitable environment for the precipitation of hardness salts as

desirable sludge materials.
B. To help the formation of Magnetite (Fe3O4) in the presence of Oxygen
scavengers (i.e. Hydrazine/Sulphite).
C. Maintain Silica in solution to prevent Silica scale formation.
8.3
CONTROLLING CHLORIDES
The Chloride value will reveal any presence of dissolved salts in the boiler. An
increase, gradual or sudden, in the level of Chlorides is an indication of contamination by sea water, and Chlorides are often used as a reference point
when controlling rate of blowdown. Too high a Chloride level indicates that
undesirable amounts of salts are present, leading to possible foaming and/or
scale and deposit formation.
30
8 / TESTS FOR BOILER WATER/LOW PRESSURE
C. Specification Control Limits.

a. P-Alkalinity: 100300 ppm (as CaCO3).
b. Chloride: 200 ppm maximum.
c. Boiler Water pH: 9.511.0 (optional).
d. Condensate pH: 8.39.0.
D. Testing preparations and equipment.
a. Boiler Water Sample preparation: Cool sample to 2025 C.
Filter as required.
b. Sample Analysis: Spectrapak 310 Test Kit
Reagents: P-Alkalinity tablets Chloride tablets.
pH strips with ranges 6.510.0 and 7.514.0.
Equipment 200 ml sample bottles.
Test procedures.
31
8.6.2 P-Alkalinity test

A. Take a 200 ml water sample in the stoppered bottle provided.
B. Add one P-Alkalinity tablet and shake to disintegrate. If P-Alkalinity
is present, the sample will turn blue.
It is essential that the condensate pH is maintained within 8.39.0. Test

this with Unitors pH paper and use Condensate Control to adjust pH
upwards if necessary.
8.6.5 Instructions Sulphite Test Kit
(optional test for low pressure single product treatment)
C. Repeat tablet addition until the blue colour changes to permanent

yellow.
Calculation:
P-Alkalinity ppm (CaCO3) = (No. of tablets used x 20) 10
For example:
If 8 tablets are used, then P-Alkalinity = (8 x 20) 10 = 150 ppm.
8.6.6 Testing procedure:

A. Take a 20 ml sample in the shaker tube supplied.
B. Add one Sulphite No. 1 tablet; shake to dissolve.
C. Add Sulphite No. 2 L.R. tablets one at a time until the sample
turns blue. Note the number of tablets used.
D. Mark the result obtained on the log sheets provided, against the
date at which the test was taken.
D. Calculate as follows:
Sulphite content = Number of Sulphite No. 2 L.R. tablets x 10.
8.6.3 Chloride test

A. For boilers under 30 bar, take a 50 ml sample in the stoppered bottle
provided.
E. After use, thoroughly rinse out the shaker tube before storage.
PLEASE NOTE! The Sulphite No. 1 tablet is used only to condition the
sample. Do not count this tablet when calculating the Sulphite level.
B. Add one Chloride tablet and shake to disintegrate; sample will turn
yellow if chlorides are present.
C. Repeat tablet addition until the yellow colour changes to
orange/brown.
Calculation:
Chloride ppm = (No. of tablets used x 20) 20
For example:
If 4 tablets are used then Chloride ppm = (4 x 20) 20 = 60 ppm.
D. Mark this result on the Spectrapak 310 log sheet, against the date
at which the test was taken.
8.6.4 pH test:
For boiler water pH test, 7.514.0.
For Condensate water, 6.510.0.
A. Take a 50 ml sample of water to be tested in the plastic sample
container provided.
B. Using the white 0.6 grm scoop provided, add one measure of the pH
reagent to the water sample, allow to dissolve stir if required.
C. Select the correct range of pH test strip and dip it into the water
sample for approximately 10 seconds.
D. Withdraw strip from sample and compare the colour obtained with
the colour scale on the pH indicator strips container.
E. Record the pH value obtained on the log sheet provided, against the
32
8 / TESTS FOR BOILER WATER/LOW PRESSURE
8.7
TEST RESULTS COMBINED TREATMENT

A. Recording Always use Unitors Rapid Response log forms to
record all readings and to keep track of all results.
1. Log form Combined Boiler Water Treatment Log, no. 310.
2. Frequency Samples should be drawn, tested and results
logged at least every three days.
B. Reporting The completed log sheet for the month should be
distributed as shown at the bottom of the form, at the end of each
month:
1. White copy to Unitors Rapid Response Centre in Norway
(address labels at back of log pad)
2. Pink copy Vessel owner
3. Yellow copy to be kept onboard
C. Evaluation
1. Logs will be reviewed at the Unitor Rapid Response Centre for
adherence to recommended specifications, with the aid of
Unitors Rapid Response staff.
2. A report letter indicating the status of the ships system, any
problems and relevant recommendations will be issued to the
ships operator.
33
9 Unitor Coordinated Treatment

Products
The use of combined product treatment for medium and high pressure boilers,
is not recommended. Because higher pressures and temperatures increase
the tendency of scaling and corrosion, which makes it necessary to have the
possibility of changing the chemical conditions and test parametres individually. The Unitor Coordinated Treatment Programme includes single function
chemicals which are dosed and monitored separately. This programme may of
course also be applied to low pressure boilers as an alternative to combined
product treatment.
9.3
OXYGEN CONTROL (HYDRAZINE, N2H4)
Hardness Control is a Phosphate powder product used in boiler water treatment to precipitate dissolved calcium hardness salts and to convert these
salts to non-adherent Calcium Phosphate sludge, which can be easily
removed by blowdown. Hardness Control is highly effective in achieving this
function; minimum dosages are required. Reduced dosage of chemicals minimises dissolved and suspended solids in the boiler water. Hardness Control
provides neutral reaction products in the boiler. A high level of dissolved and
suspended solids are the principal causes of carryover and priming.
Note here the term phosphate hide-out; as the temperature of the boiler
increases, less Phosphate can be held in solution in the boiler water. Therefore, testing and dosage of Phosphate to control hardness salts deposits
should be done when the boiler is under full load conditions. If the Phosphate
residual increases under low load conditions, this is an indication of a dirty
boiler, and increased bottom blows should be carried out to remove the sludge.
The sludge holds excess Phosphate and re-dissolves when the boiler water
temperature is reduced. For further recommendations on product dosage and
control limits, refer to the Marine Chemicals Manual.
Hydrazine is a colourless liquid at ambient temperatures, being completely

miscible with water. Its solution has an odour resembling Ammonia, but is less
pungent. It is used to efficiently scavenge and remove Oxygen from condensate, feedwater and boiler water.
Hydrazine reacts with Oxygen, acting as a scavenger. The reaction results
in Nitrogen and water, no solids being added to the boiler system.
Some of the Hydrazine will carry over with the steam, helping to maintain
the condensate pH in an alkaline range, which thereby helps combat acid
formation. Hydrazine will also form Magnetite which will act as a protective
layer against further corrosion.
Hydrazine should be added to the system using a separate dosing tank. The
tank should be filled daily with Hydrazine diluted with condensate or distilled
water. This solution should be dosed continuously to the storage section of
the de-aerator. Alternatively, Hydrazine can be fed continuously to the feed
pump suction or atmospheric drain tank over a 24-hour period.
It is important that Hydrazine should not be overdosed. At temperatures
above 270 C, Hydrazine starts to break down, creating free Ammonia.
Excessive free Ammonia and Oxygen, when combined, form a corrosive
condition on non-ferrous metals. This corrosive action can cause Copper
to deposit in the watersides of boilers, causing additional boiler problems,
as discussed earlier.
9.2
The reaction of Hydrazine in boilers

is therefore threefold:
9.1
HARDNESS CONTROL
ALKALINITY CONTROL
Alkalinity Control is used to obtain the correct pH level necessary for the
Phosphate treatment to react with Calcium salts. In addition, Alkalinity Control
is used to maintain the required alkalinity in the boiler water to prevent acid
corrosion. By adopting simple testing procedures to determine the
Phenolphthalein alkalinity (P-Alkalinity) and the total alkalinity (M-Alkalinity),
we can determine the amount of free caustic present in the boiler water by
using the formula 2(P) M = OH. If a positive number is obtained, free caustic
(OH-Alkalinity) is present in the boiler water.
34
The term excess chemicals or reserve of chemicals ensures that

chemicals are always readily available to perform their necessary functions.
For further recommendations on product dosage and control limits, refer to
the Marine Chemicals Manual.
9 / UNITOR COORDINATED TREATMENT PRODUCTS
1. It scavenges any free or dissolved Oxygen.

2. It reduces red Iron Oxide to a metal-protective black oxide coating
(Magnetite).
3. It raises the pH of the condensate reducing acid corrosion of the
condensate and re-boiler sections of the system. For further recommendations on product dosage and control limits, refer to the Marine
Chemicals Manual.
35
9.4
CATALYSED SODIUM SULPHITE (POWDER) AND CAT.

SULPHITE L (LIQUID)
Unitors Catalysed Sulphite products are used as scavengers in place of

Hydrazine where economy is of importance, or used in low pressure boilers
with open feed systems where feed inlet temperatures are low. Sulphite
combined with Oxygen forms Sulphate, which adds solids to the boiler water.
It should subsequently not be used in boilers at pressures above 30 bars
where the TDS level is critical. Sulphite is also used as a substitute for
Hydrazine when rust and scale deposits are present in boiler systems on
ships being returned to service. Hydrazine tends to remove Iron Oxide
deposits present throughout the boiler system. An amine (Condensate Control)
should be used in conjunction with Oxygen scavengers to maintain the
condensate pH within the desirable ranges throughout the entire condensate
and feedwater system.
9.5
CONDENSATE CONTROL
Condensate Control is a neutralising volatile amine recommended for use

in all boiler systems to raise the pH of condensate and steam to
a non-corrosive level (pH 8.39.0). The dosage is determined by the results
of a daily condensate pH test. Condensate Control should be dosed using
a continuous feed system. It can be introduced, using a flowmeter or
metering pump, to the condensate pump discharge, the hot well, the condensate return tank, or to the de-aerator storage tank. Condensate Control can be
dosed together with Oxygen scavengers. However, optimum control of
condensate pH is achieved by dosing separately from the Hydrazine dosage
system.
For further recommendations on product dosage and control limits, refer
to the Marine Chemicals Manual.
9.6
9.7
CHEMICAL INJECTION POINTS FOR LOW PRESSURE

Boiler systems
The following diagram depicts a typical Low Pressure Boiler System. Note
injection point for chemicals; when dosing chemicals, the recommendation to
achieve the best possible results is to always dose all chemicals in the diluted
form on a continuous basis.
1 Dosage to hot well or feed tank. All chemicals can be dosed at these points.
However, the recommended dosage of Alkalinity Control and Hardness
Control is either no. 2 feed line or no. 3 chemical feed injection directly to
the boiler. Oxygen Control and Sulphite should preferably be dosed to the
feed tank on a continuous basis.
All combined products can be dosed into the hot well.
2 Dose to injection no. 2 is required to the feed line by means of a pressure
injector or dosage pump. Dosage should be continuous, however water can
be shock treated.
3 Dosage direct to boiler no. 3. All chemicals can be dosed to this point by
means of pressure pot injector or dosage pump. Alkalinity Control or
Hardness Control is best controlled at this location and and the use of
Hydrazine, Sulphite or Condensate Control is recommended on
a continuous basis in the condensate system.
BOILER COAGULANT
Boiler Coagulant is a polymeric compound used in boilers contaminated with

small quantities of oil, or as a sludge conditioner in conjunction with the use
of Hardness Control when high levels of solids are experienced. Boiler
Coagulant should be dosed at 250cc per day. No testing is necessary if used
regularly. Daily flash blowdown is recommended to remove precipitated solids
or coagulated oil.
36
9 / UNITOR COORDINATED TREATMENT PRODUCTS
37
10 Tests for Boiler Water,

Medium Pressure
(3160 BAR)
In dosing medium pressure boilers, utilise Unitors Coordinated Boiler Water
Treatment Management Programme. This includes Alkalinity Control,
Hardness Control, Oxygen Control, Condensate Control and Boiler Coagulant.
The following tests are recommended to maintain medium pressure boiler
water within the desired level of quality when utilising Unitors Coordinated
BWT Programme are as follows:
10.3.1 Phosphate (ppm) PO4

A. Take the comparator with the 10 ml cells provided.
B. Slide the Phosphate disc into the comparator.
C. Filter the water sample into both cells up to the 10 ml mark.
10.1 UNITOR TESTS REQUIRED CONTROL LIMITS
D. Place one cell in the left-hand compartment.
1.
2.
3.
4.
5.
6.
7.
E. To the other cell add one Phosphate tablet, crush and mix until
completely dissolved.
P-Alkalinity: . . . 100130 ppm CaCO3

M-Alkalinity: . . Below 2 x P-Alkalinity
Phosphate: . . . . 2040 ppm as PO4
Hydrazine: . . . . 0.030.15 ppm as N2H4
Chlorides: . . . . . <30 ppm
pH (boil. water): 9.511.0
pH (condens.): . 8.3 9.0
10.2 UTILISE UNITORS SPECTRAPAK 311/312*/SULPHITE TEST KIT

Reagents
A. Phosphate tablets
B. Chloride tablets
C. P-Alkalinity tablets
D. M-Alkalinity tablets
E. pH papers (6.510.0 & 7.514.0)
F. pH reagent
G. Filter paper
H. Hydrazine reagent*
I. Sulphite tablets*
38
10.3 TEST PROCEDURES
F.
After 10 minutes, place this cell into the right-hand compartment

of the comparator.
G. Hold the comparator towards a light.

H. Rotate the disc until a colour match is obtained.
I.
Record the result obtained on the Spectrapak 311/312 log sheet

against the date on which the test was taken.
10.3.2 Chloride (ppm) Cl

The range of Chlorides to be tested determines the size of water sample
used. To save tablets, the use of a small water sample is recommended
when the Chloride level is expected to be high, i.e. for low Chloride
levels use 100 ml water sample, for higher Chloride levels use 50 ml
water sample. However, it should be noted that the accuracy of the test
results increases with the size of the water sample.
Equipment
A. 200 ml sample bottles
B. Lovibond 2000 comparator
C. Phosphate disc 3/70
D. 10 ml molded cells
E. Hydrazine disc 3/126*
F. Sulphite test tube*
A. Take the water sample in the stopper bottle provided.
* Optional. Either the Hydrazine Test Kit (Spectrapak 312) or the Sulphite Test Kit must be utilised.
The one to be used depends on the Oxygen scavenger in use. Please note that Sulphite is not
adviceable to use in boilers above 30 bar.
D. Count the number of tablets used and perform the following

calculation:
10 / TESTS FOR BOILER WATER MEDIUM PRESSURE
B. Add one Chloride tablet and shake to disintegrate. Sample will turn
yellow if Chlorides are present.
C. Repeat tablet addition, one at a time (giving time for the tablet
to dissolve), until the yellow colour changes to permanent
red/brown.
39
For 100 ml water sample: Chloride ppm = (Number of tablets x 10) 10

e.g. 4 tablets = (4 x 10) 10 = 30 ppm Chloride.
A. Take a 50 ml sample of water to be tested in the plastic sample

container provided.
For 50 ml water sample: Chloride ppm = (Number of tablets x 20) 20

e.g. 4 tablets = (4 x 20) 20 = 60 ppm.
B. Using the white 0.6 grm scoop provided, add one measure of the pH
reagent to the water sample, allow to dissolve stir if required.
E. Record the result obtained on the log sheet provided, against the
date on which the test was taken.
C. Select the correct range of pH test strip and dip it into the water
sample for approximately 10 seconds.
10.3.3 P-Alkalinity (ppm) CaCo3
D. Withdraw the strip from the sample and compare the colour
obtained with the colour scale on the pH indicator strips container.
A. Take a 200 ml water sample in the stopper bottle.

B. Add one P-Alkalinity tablet and shake or crush to disintegrate.
C. If alkalinity is present the sample will turn blue.
D. Repeat the tablet addition, one at a time (giving time for the tablet to
dissolve), until the blue colour turns to permanent yellow.
E. Count the number of tablets used and carry out the following
calculation:
P-Alkalinity, ppm CaCO3 = (Number of tablets x 20) 10
e.g. 12 tablets = (12 x 20) 10 = 230 ppm CaCO3
F.
Record the result on the log sheet provided, against the date
on which the test was taken.
10.3.6 Hydrazine PPM* (Spectrapak 312)

A. Take the comparator with the 10 ml cells provided.
B. Slide the Hydrazine disc into the comparator.
C. Add the water sample to both cells up to the 10 ml mark.
D. Place one cell in the left-hand compartment of the comparator.
E. To the other cell add one measure of Hydrazine powder (using the
black 1 grm scoop provided) and mix until completely dissolved.
F.
Wait 2 minutes and place the cell in the right hand compartment
of the comparator.
G. Retain the sample for the M-Alkalinity test.
G. Hold up to the light and rotate the disc until a colour match
is obtained.
10.3.4 M-Alkalinity (PPM CaCO3)
H. Record the reading shown as ppm Hydrazine.
A. To the P-Alkalinity sample add one M-Alkalinity tablet and shake

or crush to disintegrate.
B. Repeat tablet addition, one at a time (giving time for the tablet
to dissolve), until the sample turns to permanent red/pink.
C. Count the number of tablets used and carry out the following
calculation:
M-Alkalinity, ppm CaCO3 = (Number of P & M tablets x 20) 10
e.g. If 12 P and 5 M-Alkalinity tablets are used,
M-Alkalinity = [(12 + 5) x 20] 10 = 330 ppm CaCO3
40
E. Record the pH value result on the log sheet provided, against the
10.3.7 Sulphite PPM* (Spectrapak 312)

A. Take a 20 ml sample in the shaker tube supplied.
B. Add one Sulphite No. 1 tablet; shake to dissolve.
C. Add Sulphite No. 2 L.R. tablets one at a time until the sample turns
blue. Note the number of tablets used.
Calculate as follows:
Sulphite content = Number of Sulphite No. 2 L.R. tablets x 10
D. Record the result on the log sheet provided, against the date on
which the test was taken.
D. After use, thoroughly rinse out the shaker tube before storing.
Please note: The Sulphite No. 1 tablet is used only to condition the
sample. Do not count this tablet when calculating the sulphite level.
10.3.5 pH Test
7.514.0 For boiler water
6.510.0 For condensate water
10.3.8 Test results Coordinated treatment

A. Recording Always use Unitors Rapid Response log forms to
record all readings and to keep track of all results.
41
11 High Pressure
Boiler Water Control
1. Log form Coordinated Boiler Water Treatment Log, no.311/312,
or ask for special form above 30 bar pressure.
2. Frequency Samples should be drawn, tested and results logged
minimum every third day.
* This is an optional extra (to the Spectrapak 311). This test must be performed below 21 C.
A cooling coil should be fitted at the sampling point or the sample should be cooled
immediately under cold running water. Cloudy samples should be filtered before testing.
B. Reporting The completed log sheet for the month should be

distributed as shown at the bottom of the form, at the end of
each month:
1. White copy to Unitors Rapid Response Centre in Norway
(address labels at back of log pad).
11.1 TYPES OF WATER

Proper control using all aspects of your chemical treatment programme for
boilers operating above 60 bar is extremely important.
The high temperatures and pressures involved require your direct and
constant attention to the conditions in the boiler and associated equipment
in regulating the pre-treatment of the boiler water.
Unitor recommends that you test your boiler, condensate and feedwater at
least once and preferably twice a day.
The crucial aspect of controlling a high pressure boiler system is
knowing the performance of your pre-treatment equipment. The evaporator
should be producing enough high-quality distilled water to provide sufficient
composition and to handle leaks throughout the system and blowdown
requirements.
2. Pink copy vessel owner.

3. Yellow copy to be kept onboard.
C. Evaluation
1. Logs will be rewied at the Unitor Rapid Response Centre for
adherence to recommended specifications, with the aid of
Unitors computerized Rapid Response programme and staff.
2. A report letter indicating the status of the ships system, any
ships operator.
42
The efficient operation of the de-areator is critical. The function of the

de-areator is to:
A. Remove dissolved gases from the condensate.
B. Pre-heat feedwater.
C. Act as a storage tank for the boiler and suction head for the feed pump.
In many cases, improper operation of the de-areator heater will affect the
entire control and results of your chemical treatment programme. Ensure
that the Ammonia level is being kept below a maximum level in the
condensate of 0.3 ppm at all times and the feedwater indicates less than
10 ppb dissolved Oxygen. Be certain to maintain proper operating temperatures and pressures in the de-areator. Temperature variations between
the upper and lower sections of the de-areator indicate faulty operation
of the unit.
To help resolve a condition where Ammonia levels exceed the allowed
limit of 0.3 ppm, the de-areator should be vented to the atmosphere.
Controlled venting is critical to ensure that excess water and heat are
not lost to the atmosphere to reduce your Ammonia level below the
maximum allowable level. At times, the efficiency of the gland exhaust
condenser re-dissolves the gases which are intended to be vented off to the
atmosphere and which continually attributes to the build-up of the Ammonia
43
levels in the condensate. Of course, precise control and dosage of Hydrazine

is critical in controlling this factor. Overdosage of Hydrazine will greatly affect
the build-up of Ammonia in your system. Always dose enough Hydrazine to
react with the trace amounts of Oxygen left in your feedwater after
deaeration. Unitor recommends a 0.05 ppm residual of Hydrazine in your boiler
water. However, theoretically, any test results above 0.03 ppm will indicate
the presence of Hydrazine and this is an adequate residual to assure Oxygenfree boiler water.
Controlling the pH and Phosphate coordination of the boiler water is also
very critical. The coordination of the dosage of these products will prove to
maintain your internal boiler surfaces free from caustic embrittlement
corrosion and deposition.
Unitors high pressure coordinated pH-Phosphate boiler water treatment
programme is designed to maintain your boilers in optimum condition. If you
experience any difficulties in controlling the programme prescribed herein,
contact your local Unitor representative.
Lastly, a routine for set periodic blowdown will enhance the results of this
boiler water treatment programme. Even if test results are within good range
of the recommendations, sludge is forming in the boiler at all times. This is
a normal reaction of the chemicals you are treating. Plan a schedule that
will fit into the vessels normal operating procedures to allow a complete
blowdown procedure, including a bottom blow and a blow of each header
and to remove the sludge build-up. Unitor recommends that this routine be
performed twice a day. Of course, if conditions warrant it, additional blows
should be performed.
SPECTRAPAK TEST
UNITOR TREATMENT
Water to be
analysed
Spectrapak
water analysis
Control
limits
Unitor
treatment
products
Feedwater
Hardness
Oxygen (optional)
Chlorides
0
< 10 ppb
< 5 ppm
Oxygen Control
Boiler water
P-Alkalinity
M-Alkalinity
pH (coordinate)
Phosphate (coordinate)
Hydrazine
Chlorides
Silica
Cond.
Reference
Reference
9.610.2
1025 ppm
0.050.10 ppm
< 20 ppm
< 3 ppm
< 300 S/cm
Alkalinity Control
Alkalinity Control
Alkalinity Control
Hardness Control
Oxygen Control
Condensate
pH
8.39.0
Chlorides
Ammonia
< 5 ppm
< 0.3 ppm
Condensate
Control
11.3 TESTING HP BOILER WATER TEST KIT PC 22 PHOTOMETER

11.2 TREATMENT PROGRAMME FOR BOILERS OPERATING
IN THE RANGE OF 6083 BAR
Unitor recommeds the use of coordinated Phosphate/pH water
treatment control.
The following high pressure boiler programme is based on the pressures,
temperatures and operating conditions of boilers operating in the range of
6083 bar. Maintaining the chemical concentrations and parameters
prescribed will protect your boiler system. The following are specific control
parameters and products required.
44
11 / HIGH PRESSURE BOILER WATER CONTROL
PC 22 LED filter photometers are micro-processor controlled and have been

specially designed for this purpose. Production using the most modern SMD
technology, ergonomically-styled housing and the robust character of the
instruments guarantees high precision in analysing in laboratories as well as
using the instruments in the field.
The four-line display enables the clear indication of the complete date
setting and an exemplary users direction.
System Specifications
The PC 22 Photometer combines the sum of experience, determined by the
daily experience which establishes precise measurement results within
a short period.
The aspects of compact measurement, ergonomical operation, modern
design and a high measure of spraywater protection were taken into account
in designing the housing.
The foil keyboard, which incorporates an acoustic feedback via a beeper,
is scratch-resistant and acid/solvent-resistant. The electronic components
are sealed to provide maximum protection against corrosion.
45
Delivery Contents of SPEKTRAPACK PC 22

1
1
1
1
4
1
4
1
1
1
1
1
1
Ph-meter
PC 22 Photometer in a case
9 V-Battery
12 V-Mains adapter
Cells
Conductivity meter
Stoppers
Measuring cylinder 100 ml
Test tube brush
Stirring rod
Cleaning kit
Manual
Guarantee-Certificate
Reagents
Ammonia
Silica
P-Alk
M-Alk
Hardness
Phosphate
Hydrazine
Chloride
Optional dissolved Oxygen test. The set is very easy to use and gives a quick
accurate answer. The test results given can easily be compared with
similar equipment in a lab.
(Unitor recommends using the Chemetrics dissolved Oxygen test. Consult
the Unitor office to arrange availability.)
11.3.1 Spares
Standard spares are available from your local Unitor Marine Chemical
representative. Order all spares from the on-going supply list provided
with these test instructions. A Replacement Tablet Reagent Pack.
Estimate 3-monthly requirements.
11.3.2 Safety
Reagents are for chemical testing only; not to be taken internally. Keep
away from children. Wash hands after use.
condensate water. High pressure boiler water using the

co-ordinated Phosphate-pH control method should always be
tested using the pH meter for accuracy and the best results.
Note: Never touch the pH electrode sensor. Always rinse the
sensor in untreated distilled water after use and keep the sensor
damp. Store in distilled water.
To use, follow the manufacturers instructions provided with the
instrument. Calibration and slope adjustment can be checked using
pH 7 and pH 10 buffers.
G. Conductivity Meter.
Note: Existing pH and conductivity meters can be used if onboard.
Also verify test reults by standard solutions, pH buffer solutions or
laboratory verification.
H. Ammonia.
I.
Hardness.
J. Dissolved Oxygen (optional). Testing feed water for dissolved

Oxygen entering the boiler may be conveniently analyzed by inserting Oxygen ampoule into a flowing stream of the sample. Feedwater
should be allowed to flush from sample line for a minimum of
10 minutes before taking sample. When the ampoule tip is snapped,
vacuum inside the ampoule pulls the sample in where it mixes with
the pre-measured reagent inside. A deep reddish/violet
colour forms proportional in intensity to the dissolved Oxygen
content of the sample. After inverting the ampoule several times to
mix the contents, compare that colour with the liquid colour
standards in the kit to determine the concentration of Oxygen.
K. Silica.
L. Boiler pH.
M. Condensate pH.
11.3.3 High Pressure Procedures

A. Phosphate.
B. P-Alkalinity.
C. M-Alkalinity.
D. Chloride (Boiler and Condensate Water).
E. Hydrazine.
This test should not be performed at a temperature above 21 C.
A cooling coil should be fitted at the sampling point or the sample
should be cooled immediately under running water. Cloudy samples
should be filtered before testing.
F. pH (Boiler and Condensate Water). The electronic pH meter is the
most accurate and reliable method of testing high purity boiler and
46
11.4 TEST RESULTS HIGH PRESSURE BOILER WATER TREATMENT

11.4.1 Recording
Always use Unitors Rapid Response log forms to record all readings
and to keep track of all results.
A. Log form Ultra High Pressure Boiler Water Treatment Log, no. 314.
B. Frequency Samples should be drawn, tested and results logged at
least once per day.
11.4.2 Reporting
The completed log sheet for the month should be distributed as shown
at the bottom of the form, at the end of each month:
47
A. White copy to Unitors Rapid Response Center in Norway

(address labels at back of log pad)
11.5.2
Coordinated phosphate/pH treatment system
B. Pink copy Vessel owner

C. Yellow copy to be kept onboard
11.4.3 Evaluation
A. Logs will be reviewed at the Unitor Rapid Response Centre for
adherence to recommended specifications.
B. A report letter indicating the status of the ships system; any
ships operator.
11.5 INTERPRETING TEST RESULTS

11.5.1 Hydrazine testing and control
For reasons of economy, try to minimise the quantity of Hydrazine
employed to scavenge Oxygen as well as reducing the amount of
Ammonia that will be formed by the breakdown of Hydrazine. Ammonia
in the presence of Oxygen is corrosive to Copper and Copper alloys
(non-ferrous alloys).
It will be necessary to test the Hydrazine residuals in the boiler daily
in order to obtain complete protection with minimum doses of Hydrazine.
If the Hydrazine residual in the boiler is over 0.1 ppm, reduce the
dosage of Hydrazine until the boiler Hydrazine residual falls below the
recommended maximum of 0.1 ppm. If the Hydrazine residual does not
immediately drop below the 0.1 ppm level, the boiler should be blown
down to reduce the Hydrazine level. New boilers, or those recently
open for inspection and repair, may take several weeks to achieve a
normal boiler Hydrazine residual due to oxides. This is normal, and until
a Hydrazine residual is obtained in the boiler water, test the feedwater
for the Hydrazine content. Maintain the Hydrazine reading in the feedwater between 0.02 and 0.03 ppm. No Oxygen is entering the boiler with
the feedwater when Hydrazine is present in the water. However,
be certain not to exceed the max. level of 0.1 ppm in boiler water.
Hydrazine may be dosed into the feed pump suction, or preferably,
to the storage section of the de-aerator, which will maximize the
residence and reaction time of Oxygen control.
A separate dosing tank and pump set should be used for dosing
Hydrazine to the system. (Condensate Control may be fed with the
Hydrazine.)
The estimated daily dose should be mixed with condensate and the
pump should be set to deliver the daily dosage over an entire
24-hour period.
48
If a pump and tank set is not available, Hydrazine (and Condensate

Control) can be added to the system through a tank and flowmeter into
the atmospheric drain tank, with injection point well below the water
level of the tank.
Most boiler treatments use Sodium Hydroxide to produce the
required alkalinity in the boiler water. This procedure is often called
The Free Caustic Regime, which means that if a sample of the boiler
water were evaporated to dryness in an inert atmosphere, the remaining solids would contain Sodium Hydroxide.
High concentrations of Sodium Hydroxide can cause inter-crystalline cracking and, in high pressure boilers operating with a high heat
flux, caustic gouging can occur. Caustic gouging is a reaction between
Sodium Hydroxide and iron to form Sodium Ferrate. Nascent Hydrogen
is liberated by this reaction and can cause Hydrogen embrittlement of
the steel; often the embrittlement occurs simultaneously with the loss
of boiler metal due to gouging. To prevent this from occurring, a coordi-
49
nated phosphate to pH ratio method is used to produce the alkalinity

required to protect the boiler steel from corrosion.
The method of control, in practice, is to determine the pH of the
boiler water and the Phosphate ppm level. These figures are then
checked against the graph. If the intersection of Phosphate/pH values
falls within the parallelogram zone or below the curve, no free Sodium
Hydroxide will be present, which is the desired situation.
If the pH is high according to Phosphate/pH chart, blow down to
reduce it to the appropriate range, which also reduces the Phosphate
level. If the pH is low and the Phosphate reading is in the proper range,
add Alkalinity Control. If the Phosphate reading is below the recommended limits, add Hardness Control only. This procedure will also
reduce the pH. If the Phosphate reading is high, blow down to the
correct level. The correct balance of Phosphate to pH, to eliminate free
Caustic, is easily achieved with the use of quality distilled feedwater.
When both Alkalinity Control and Hardness Control are required, raise
the Hardness Control before the Alkalinity Control.
NOTE: Balance of Phosphate/pH to eliminate free caustic is easily achieved with the use of
distilled (evaporated) feedwater. If raw or contaminated water is employed, it may
be difficult or impossible to achieve a proper balance.
11.6 UNITOR TREATMENT CHEMICALS DOSAGE GUIDES

11.6.1 Hardness Control Dosage Guide
Phosphate test
Hardness control
Result ppm
gr/ton
0 5
20.77
510
16
1015
11
1520
No Dose
2025
No Dose
25 and above
Blow down
11.6.2 Alkalinity Control Dosage Guide
pH test
Alkalinity control
result ppm
ml/tonne
8.4
18
8.6
17
8.8
17
9.0
16
9.2
16
9.4
15
9.6
13
9.810.2
Satisfactory
10.3 and above
Blow down
50
11.6.3 Oxygen control Dosage guide

Hydrazine test results
Oxygen control
Less than 0.05 ppm
Increase dosage 25 %
0.050.10 ppm
Maintain dosage more than
0.10 ppm
Decrease dosage 25 %
Note:
Adjustment
Bear in mind that variations in plant loads and the efficiency

of the de-areateor will affect the actual dosage of Hydrazine.
11.6.4 Condensate control Dosage chart

Litres per 10 tonnes Boiler Water Capacity
Condens. pH Less than 8.3
8.39.0
over 9.0
Dosage
Increase by 25 % Maintain daily Reduce by 25 % every
ltr/day
every 72 hours
dose 0.75 ltr
72 hours
11.6.5 Initial dosage for each ton capacity boiler water
HARDNESS CONTROL
23 gr/tonne
ALKALINITY CONTROL
180 ml/tonne
OXYGEN CONTROL
120 ml/tonne
CONDENSATE CONTROL
0.75 ltr/day
Note:
All dosage recommendations given above are estimations only, will vary depending
on local conditions as makeup water quality, type of boiler and boiler load.
Water treatment on-going supply list 6 months estimate
11.7 RECOMMENDED DOSAGE POINTS FOR MEDIUM PRESSURE

AND HIGH PRESSURE CONDENSATE AND
FEEDWATER SYSTEMS
11.7.1 Hydrazine
Continuous to the storage section of the de-aerator.
11.7.2 Condensate Control
Should be dosed to the condensate system on a continuous basis.
Note:
The testing point for Condensate pH should be up-stream (before) from the dosage
point of Condensate Control.
For steam vessels, separate dosages of Oxygen Control and

Condensate Control are recommended for better individual control of
each chemical. However, if only one dosing unit is available, both
Oxygen Control and Condensate Control can be dosed together.
Hydrazine and Condensate Control are compatible with each other.
51
12 Boiler Wet Layup

11.7.3 Recommended Sampling Points
Point (A) Condensate pH, Ammonia, Chlorides.
Point (B) Feed Water Dissolved Oxygen, pH, TDS, Chlorides.
Note:
Testing can be done at the discharge from the feed pump. However, if high
dissolved Oxygen residuals are found, water in the storage area of the de-aerator
should be checked to ensure no air is leaking into the feed pump.
Boilers are likely to suffer more from corrosion during periods when not in use
or laid up. They must be protected. Proper layup procedures are essential.
Corrosion will occur if :
A. Low pH conditions occur.
B. Oxygen is present in the boiler water.
The procedure starts 23 days before the layup date
1 Test the boiler treatment levels and blow down the boiler at regular intervals to reduce potential sludge. The boiler should not be laid up dirty.
2 Raise the treatment levels for alkalinity to the maximum allowable level for
that boiler pressure.
3 The boiler should then be treated with a high level of Oxygen Control after
it has been isolated from the main steam line. Gentle firing of the boiler
should be used to fully circulate the treatment with the boiler vented.
150200 ppm Hydrazine is dosed into the boiler. (This works out at
1.25 litres/tonne of water.)
NB! Full water capacity must be used to calculate this not working capacity.
4 The vent cock on top of the boiler should be opened and the boiler filled
with feedwater that is as hot as possible (90 C).
5 The boiler should be given a headof water to ensure that the boiler is kept
full of water. This is achieved by connecting a hose of a drum of treated
water to the boiler vent cock to make up for any losses due to leaks.
6 Where super heaters are in place, the manufacturers instructions must
be followed.
7 This principle of wet layup can be used for exhaust gas economisers, etc.
8 Wet layup of boilers is for the short term. A different procedure should
be used for a long term layup .
Returning to Service
Drain the boiler of excess Hydrazine, refill with water and warm through in the
normal way.
52
53
13 Boiler Blowdown
Blowdown is the mechanical process employed to remove and lower
excessive concentrations of dissolved and suspended solids in boiler water.
This procedure must be exercised on a regular basis to prevent solids from
building up which in turn can result in steam carryover leading to contamination of the after-boiler system. In addition, the consequential concentration
and accumulation of sludge and scale in the boiler can cause heavy deposits
to collect on heat exchange surfaces. Once formed, these deposits reduce
heat transfer and restrict water circulation, causing the boiler to operate at
less than its optimum design efficiency. In order to compensate for the loss
in thermal transfer, the fuel consumption must be increased to raise the
temperature on the furnace-side of the boiler. This in turn can cause
overheating and tube failure.
In general, most feedwater and makeup water is processed and monitored
prior to entering the boiler to ensure that the concentrations of naturallyoccuring solids are at a minimum. If done properly, only small amounts of
these contaminants are allowed to get through. These, however, will
concentrate in the system and therefore must be dealt with by the addition
of water treatment chemicals.
Solids concentrations in boiler water are usually determined by
a conductivity meter which displays a visual readout of the ability of the
boiler water to transmit an electrical current. This characteristic, called
the specific conductance, is directly related to the solids content of the
solution being measured. The greater the solids concentration, the higher
the reading. The scale on the meter usually measures the results in units
of electrical conductance as either siemens or microohms per centimeter
at 25 C. This value can be multiplied by a specific factor to determine
the dissolved solids concentration. Some meters have scales that read
directly in parts per million of total dissolved solids. Thus, these devices
are called both conductivity and TDS meters. In some systems, these
meters are permanently installed to continuously monitor boiler,
condensate and feedwater. Understand and know the conductivity meter
you are using.
An upper limit for the maximum allowable concentration of dissolved
solids is usually specified for a system based on the characteristics of
that system. Operational temperature and pressure are normally given
primary consideration. The higher the value of these parameters, the
lower the tolerance of the system for dissolved and suspended solids and
therefore the lower the specification limit. Once this value has been
reached or exceeded, the system must be blown down to reduce the solids
content as much as possible without sacrificing other aspects of the
system operation.
54
13 / BOILER BLOWDOWN
The Chloride residue is used as a reference value for the TDS level, and is
used to determine blowdown requirements. An upper Chloride concentration
limit is prescribed for the system being monitored.
Blowdown as percent is expressed as:
Cl in feedwater x 100
Cl in boiler.
= % Blowdown
A bottom blowdown may be done to rapidly remove high solids content in

the boiler water. Continuous or intermittent surface blowdown may be used to
achieve controlled reduction of TDS. The method used is usually dictated by
the severity of the contamination and the conditions of the specific system
involved. Observe all manufacturers recommendations for blowdown
procedures as improper procedures can be detrimental to the boiler.
Therefore, the process used must be implemented and performed
judiciously, bearing in mind all parameters of the system (i.e. available
makeup water, available chemicals, boiler load requirements, etc.).
EXCESSIVE BLOWDOWN WASTES WATER, HEAT & CHEMICALS.
Dumping the Boiler
Occasionally it may be necessary to remove the entire contents of the waterside of the boiler system, or to prepare the unit for dry layup when it is to be
decommisioned for an extended period of time. The boiler must never be
emptied while the system is still hot, as this can cause solids to bake onto the
hot surfaces, forming deposits which are extremely difficult to remove. Since
the boiler internals retain heat for a considerable period of time after the
system is taken off line, a wait of at least twenty-four hours is recommended
from when the unit is shut down before commencing the dumping process.
55
14 Chemical Cleaning of Boilers

Many different types of contaminants can be found in the waterside of
a boiler system. These can originate from impurities naturally found in or
added to the water or from extraneous materials which have gained entrance
due to faulty, worn or defective equipment associated with the system. This
contamination can be in the form of hardness scale, oil, metallic oxides,
sludge and various combinations of these as well as other miscellaneous
materials. The procedure(s) required to clean the system will therefore
depend on the nature and condition of the substances to be removed.
The best initial approach to chemical cleaning is to inspect the fouled system
as thoroughly as possible to determine the nature and extent of contamination.
If possible, samples of the offending materials should be taken for examination
and if necessary sent in for laboratory analyses. Once the results of this preliminary investigation and/or lab analysis are known, the appropriate cleaning
procedure or procedures can be determined and implemented as follows.
J. During this period, make short blowdowns from drums and headers,
adding water as necessary to maintain the initial level.
K. After twenty-four hours, shut down the boiler and allow to cool until
the pressure drops to zero.
L. Open all vents and drains and allow boiler to drain.
M. While draining, or as soon as possible after draining, flush the boiler
with high-pressure, hot, fresh water.
N. Inspect the system, removing any sludge or scum which may have
accumulated during the cleaning process.
O. If results of the cleaning are unsatisfactory, repeat the procedure.
P. Secure boiler and return to service.
Q. If system is to be laid up, do so in accordance with recommended
wet or dry procedure.
14.1 BOILING OUT PROCEDURE

14.1.1 Parameters
A. Pre-commission cleaning of new systems to remove preservatives,
mill scale and other contaminants of construction.
B. Subsequent to major system repairs, prior to returning to service.
C. Removal of trace amounts of oil contamination.
14.1.2 Procedure
A. Mechanically remove as much oily matter and as many other loose
contaminants as possible.
B. Fill the boiler to about one half its capacity with hot fresh water.
C. Add Unitor Alkleen Safety Liquid at the rate of 15 litres/tonne of
boiler capacity.
D. Secure manhole openings and fill boiler to normal steaming level.
E. Open drum vents and drains on superheater outlets.
F. Carefully and slowly commence firing while maintaining below
operating conditions.
G. When steam begins to appear at vents, close vents and superheater
inlet drain. Leave outlet drain or outlet vent slightly open.
H. Allow pressure in the system to increase at a rate no greater than
7 kg/cm2 per hour until one half of normal operating pressure or
maximum 21 kg/cm2, whichever value is lower, is reached.
I. Maintain this condition for at least twenty-four hours, if necessary
by intermittent firing of the boiler. Do not exceed originallydetemined cleaning pressure.
56
14 / CHEMICAL CLEANING OF BOILERS
14.2 DEGREASING PROCEDURE

For removal of light to heavy contamination resulting from ingress of oil due to
defective machinery, equipment seals, or bunker or cargo tank heating coils.
A. Determine the source of oil contamination and take appropriate steps to
eliminate the problem prior to initiating the cleaning operation.
B. Inspect boiler interior as thoroughly as possible to determine the approximate degree of contamination (i.e. light, moderate, heavy). While boiler is
open, muck out as much oil and oily sludge found in boiler as possible
before closing the boiler up. You are also recommended to plug down
comers, if present, to allow circulation through main tubes of boiler. Install
external circulation pump to circulate cleaning solution from water drum
back to steam drum. Make all necessary connections.
C. Secure inspection access openings and introduce the appropriate amount
of Tankleen Plus and fresh water based on the estimated degree of contamination as follows. Ensure all boiler internals needed to be cleaned.
Degree of
Contamination
Light
Moderate
Heavy*
% by Volume of
Tankleen Plus in Water
12 %
23 %
35 %
* If contamination is particularly heavy, Tankleen Plus can be substituted

by Carbon Remover at the rate of about 10 % by volume.
57
D. If circulation pump is being used, start circulating solution. Fire the

boiler for about 5 minutes, then secure for 1520 minutes. Continue
this process until the water temperature reaches 5060 C. Do not
allow the temperature to go above 60 C. Continue this operation
for about 12 hours.
E. Drain the boiler.
F. Rinse thoroughly with high-pressure water (with heat if available).
G. Drain and inspect as thoroughly as possible.
H. If necessary, repeat steps 3 through 7.
I. Secure all access openings and fill with feedwater. Remove plugs from
down comer if this method was employed.
J. Startup initial dosage of treatment chemicals and initiate boiler operation.
K. Monitor treatment residuals and adjust as necessary to bring boiler
water treatment programme employed into proper specification.
L. Add 250 ml Unitor Boiler Coagulant every 12 hours and increase blowdown
to remove any excess oil that remains for at least one week after the unit
is returned to service.
G. Continually check temperature and pH of the solution at regular intervals.

Maintain temperature as previously indicated. If pH goes above 4, add
additional Descaling Liquid or Descalex. When using Descalex, take
sample of original solution to compare with later samples. If solution
changes to a yellowish colour, additional Descalex is required.
H. When the circulation period is complete, drain the system and rinse
thoroughly with fresh water to remove any excess debris.
I. Neutralise any remaining traces of acid by circulating a 0.5 % solution of
Alkalinity Control through the circuit for 24 hours.
J. Drain the neutralizing solution, checking the effluent to ensure it has
a pH of 7 or greater. If not, repeat steps 9 and 10.
K. Re-inspect system interior and if necessary repeat steps 2 or 3 through
11 as indicated.
L. Remove by-pass connections, secure all access openings and fill with
feedwater.
M. Add start-up dosage of treatment chemicals and initiate boiler operation.
N. Check for proper treatment residual levels, adding additional chemicals if
necessary to bring within proper specification limits.
14.3 DESCALING AND DERUSTING PROCEDURE
Refer to Descalex and Descaling Liquid Product Data Sheet for additional
information.
A. Inspect boiler interior as thoroughly as possible to determine degree of

contamination (i e. light, moderate, heavy).
B. If deposits are covered with an oily or greasy film, degrease as outlined in
steps 1 through 8 of Unitors degreasing procedure (previous, this section).
C. Subsequent to degreasing or, if not required, construct a circuit for
recirculating the acid cleaning solution through the boiler, being certain to
by-pass all sections of the system containing non-ferrous metals. Ensure
this circuit is vented at its highest point to allow the release of gases
produced during the cleaning process.
D. Introduce a solution containing the appropriate amount of Descalex or
Descaling Liquid mixed with fresh water, based on the estimated degree of
contamination as follows:
Degree of
Contamination
Descaling Liquid
in Water
Descalex
in Water
Light
Moderate
Heavy
510%
1015%
1520%
35%
510%
1015%
E. The descaling process can be accelerated by controlled heating of the

cleaning solution. This must be done with great care, never allowing the
solution temperature to exceed 60 C.
F. Circulate for 412 hours depending upon the degree of contamination.
58
14 / CHEMICAL CLEANING OF BOILERS
59
15 Diesel Engine
Cooling Water Treatment
15.1 PROBLEM AREAS
There are four key areas which must be considered when treating diesel
engine cooling water systems.
15.1.1 Scale
Scale results when a compound precipitates from the water phase
because its solubility has been exceeded. Scale is a dense, adherent
deposit of minerals and is tightly bonded to itself and to metal surfaces.
Scale forming on metal surfaces requires four simultaneous factors:
A.
B.
C.
D.
Exceeding the solubility of the compound in water.

Formation of small nuclear particles.
Adequate contact time for crystal growth.
Scale re-deposition exceeds the rate of dissolution.
One primary factor influencing scale adherence is surface roughness.

The rougher the surface, the greater the probability of adherent scale
forming. Also, scale forms more readily on corroding surfaces than on
non-corroding surfaces. Easily corroded metals (mild steel) result in
significantly more scale than metals that do not corrode (stainless
steel).
In addition to the four primary factors influencing scale deposition,
there are other factors that offset the formation of scale. Wildly
fluctuating pH is a significant cause of scale deposition in closed loop
systems. Unitor uses Borates to buffer and control this fluctuating pH.
As the pH of the system increases, so does the scaling potential for
almost all common scale. This would include Calcium Carbonate,
Calcium Sulphate, and Iron Oxide. Low pH extrusions can accelerate
corrosion, provide nucleating sites and increase the potential for some
forms of Silica scale.
Scale formation in diesel engine cooling water systems can be
controlled by various methods. Removing scale-forming Ions from the
water before that water enters the cooling system is the most effective
method. Almost all engine manufacturers recommend the use of
distilled water. Distilled water is free of minerals. However, it is
aggressive water and, if untreated, can lead to corrosion.
15.1.2 Corrosion
Corrosion is the phenomenon that returns metals to their native states
as chemical compounds or minerals.
60
15 / DIESEL ENGINE COOLING WATER TREATMENT
In diesel engines containing dissimilar metals, our concern is

galvanic corrosion. When exposed to water, one metal becomes anodic
and the other cathodic, setting up a galvanic cell. For example, when
Copper and Mild Steel are connected in water, the Mild Steel becomes
the Anode, because it will give up electrons more readily than the
Copper. The metal loss occurs at the anode, so the Mild Steel corrodes.
Unitor recommends the use of a corrosion inhibitor containing Nitrite,
Borate and Azole. Nitrite protects Mild Steel and Iron, while Azole
protect Copper from corrosion. Nitrite acts by forming a protective
metal oxide (passivating film) on the metal to be protected.
15.1.3 Fouling
Fouling is different from scaling in that fouling deposits are formed from
material suspended in the water, while scale deposits are formed from
minerals in solution. Materials that cause fouling in cooling water
systems are suspended solids and oil leaking into the system. We must
control fouling in a diesel engine cooling water system, as it interferes
with the effectiveness of corrosion inhibitors.
15.1.4 Microbiological activity
Nitrites act as a food source for some types of bacteria. While the
presence of bacteria is not as widespread in diesel engine cooling
water systems as in other cooling water systems, it is a potential
problem. The problem becomes apparent when conducting chemical
tests of the cooling water. If the personnel on the vessel are dosing
Nitrites and do not get a reading and the pH begins to fall, there is a
possibility of microbiological activity. This can be verified by simple test
methods (dip slides), or by sending a sample of the water to Unitor.
15.2 UNITOR COOLING WATER TREATMENT PRODUCTS

Diesel engines have almost completely replaced turbines as the main
propulsion unit in ships. These engines need to be cooled and water is used
for this purpose. This water must be conditioned to ensure that scale does not
deposit on the heat transfer surfaces in the cooling system.
15.2.1 The System
The water is circulated around the engine and any loss due to leaks,
etc. is made up from the expansion tank. As it circulates through the
engine cooling spaces, the water picks up the engine heat, and this hot
water goes to a heat exchanger where it is cooled.
61
The steam heater is used to warm the engine up from cold. An air
separator is normally installed to get rid of entrained air in the system.
The water added to the expansion tank is termed make-up water.
Distilled water shall preferably be used for these cooling systems.
This is normally made onboard by a fresh water evaporator (or
generator). A useful way of increasing the plant efficiency is to utilise
the heat taken from the engine to provide a heat source to the
evaporator.
If evaporated water cannot be used for make-up, then fresh shore
water will have to be used. This is normally much higher in impurities.
The engine water temperature is in the region of 65 C to 75 C at the
inlet to the engine. It is maintained at this temperature by controlling
the cooling. The cooler is bypassed if the temperature drops.
15.2.2 Corrosion
As mentioned above, this is the main problem in diesel engine cooling
systems. The water contains some Oxygen, and if it is untreated, an
ideal environment will exist for all types of corrosion.
15.3 DIESELGUARD NB AND ROCOR NB LIQUID

15.3.1 How do they work?
All the information is contained in the relevant product data sheets but
can be summarised as follows:
They provide a very thin coating to all metal surfaces to prevent the
corrosion from starting. The water is also made alkaline by the treatment to ensure that there is no acid corrosion.
It is important that there is an excess of treatment in the system to
replace any breakdown in the coating and to treat the makeup water as
it enters the system.
The testing for this is quickly carried out by the Spectrapak 309
Cooling Water Test Kit.
The chart below can be used to determine the dosage requirement

necessary to achieve a nitrite residual level between the minimum
and maximum specification range limits.
Nitrite (as ppm NO2)
180
360
540
720
900 1080 1260 1440 16202400
Dieselguard NB Kg/1000 L 2.88 2.52 2.16 1.80 1.44 1.08 0.72 0.36
15.3.3 Rocor NB liquid dosage chart

Unitor Rocor NB Liquid
A.
Initial dosage for an untreated system is 9 litres/1,000 litres of
distilled water. This will bring the treatment level up to a minimum
level of 1000 ppm.
B.
The chart below can be used to determine the dosage requirement necessary to achieve a Nitrite residual level between the
minimum and maximum specification range limits.
Nitrite (as ppm NO2)
Rocor NB Liquid L/1000 L 13.0

Note:
180
360
540
720
900
11.3
9.7
8.1
6.5
4.9
1080 1260
3.3
1.7
14402400
0
When initially dosing a cooling water system, it is typical that the initial dosage may
vary from vessel to vessel, or system to system.Total passivation of the cooling
water system will consume more product than when making Nitrite up as maintenance dosages. The quality of make-up water will also affect initial dosage rates.
Some points to note:

All cooling water treatments must be approved by accepted
Government bodies for use where the water is used as a heat
source for an evaporator making drinking water.
The treatments must also be accepted by the engine manufacturer.
The Unitor products are covered in these areas.
15.3.2 Dieselguard NB dosage chart
Unitor Dieselguard NB
Initial dosage for an untreated system is 2 kg/1,000 liters of makeup
water. This will bring the treatment level up to a minimum level
of 1000 ppm.
62
63
15.4 TESTS FOR DIESEL ENGINE COOLING WATER TREATED WITH

DIESELGUARD NB/ROCOR NB LIQUID
The following tests are recommended to maintain cooling water within the
prescribed limits when using Dieselguard NB/Rocor NB Liquid:
1. Nitrite
2. pH
3. Chlorides
10002400 ppm as NO2

8.310.0
50 ppm maximum
15.4.1 Nitrite Recommended Limits 10002400 ppm as NO2

The Nitrite concentration should be maintained within the above
recommended limits to effectively inhibit any corrosive or scaling action
within a closed cooling system. Over-concentration should be avoided
to minimise the cost of maintaining the system. Under-dosage can set
up a condition where accelerated corrosion can occur in areas which
become unprotected. Dieselguard NB/Rocor NB Liquid is dosed
according to the recommended nitrite level.
15.5 SAMPLING OF DIESEL ENGINES:

Accessible sampling cocks should exist on all cooling systems for each diesel
engine. This including, but not limited to, main jacket water, piston cooling,
fuel oil valve, auxiliary engines, low temperature systems, etc. A representative sample must be taken from each cooling water system to be tested.
To minimise the effort in obtaining cooling water samples, a sample cock
located in a position to draw a sample/having access to draw the sample
quickly and easily will make the task of drawing samples a simple one.
In each case of drawing a sample, the container should be filled with the
water to be tested, then sealed and labelled. It is advisable to conduct the
appropriate tests within 30 minutes of drawing the sample, although this time
limit can be extended when sample container is completely filled and sealed.
15.5.1 Sampling Procedure:
The suggestion is for one sample bottle for each system to be tested.
Mark each bottle clearly for each system.
A. Provide a clean bottle for each sample drawn:
15.4.2 pH Recommended Limits 8.310

The effectiveness of a corrosion inhibitor is restricted to within a
certain pH range. Treatment with Dieselguard NB/Rocor NB Liquid
ensures that this pH range is observed when the Nitrite level is
sufficiently maintained to prevent corrosion. Under certain conditions
because of external contamination, the pH may not fall into the range
usually found with the correct Nitrite dosage. In such cases, Unitor
recommends dosing 50 ml of Unitors Alkalinity Control per tonne of
cooling water to raise the pH value when the pH is below 8.3. Re-test
pH after dosage to prove that the pH value is being maintained between
8.3 and 10.0.
The bottle should contain 0.5 litre, should be made of glass or

plastic, have a screw cap that seals air-tight and a label indicating
pertinent data:
a. Nature of water sample:
1. High temperature system
2. F.O. valve
3. Piston
4. Auxiliary
5. Low temperature system
b. Sampling point/location
15.4.3 Chlorides Recommended limit max. 50 ppm

The Chlorides value of the cooling water should be kept as low as
possible. Any increase in value whether sudden or gradual, will be an
indication of sea water contamination. Check with the engine manufacturer for other specified limits.
If the Chloride level exceeds 50 ppm, the possibility of corrosion in
the system increases because Chlorides have a negative effect on the
passivation film created by nitrites. Therefore, until corrective action
has succeeded in bringing the Chloride level back down below 50 ppm,
the nitrite level should be kept close to the upper limit (2400 ppm).
15.4.4 Sampling and testing of cooling water
Samples should be drawn, tested and results logged for each system at
least of once per week and if possible six times per month.
64
B. Allow effluent to flush through sampling line a minimum of three

to five minutes.
C. Cool effluent to less than 25 C before commencing to draw sample.
D. Rinse bottle at least three times with sample water.
E. Secure cap on bottle air tight.
F. Be sure sample is representative of total coolant in system.
G. Draw sample from same point in the system each time.
H. Sample should be analysed as soon as possible after securing.
65
15.6 TEST EQUIPMENT UNITOR SPECTRAPAK 309

TEST KIT TEST PROCEDURES
15.6.1 Sample preparation:
A. Cool sample to 2125 C
B. Filter if necessary to clarify.
15.6.2 Spectrapak 309 content:
A. Reagents:
a. Nitrite No. 1 tablets
b. Nitrite No. 2 tablets
c. Chloride tablets
d. pH test strips (6.510.0)
B. Equipment:
a. Syringe
b. Plastic sample container
15.6.3 Test methods:
A. Nitrite test
a. Take a 5 ml water sample with the syringe and put into the
container provided.
b. Make the sample up to 50 ml using distilled water.
c. Add two Nitrite No. 1 tablets and shake to disintegrate (or crush
with the rod provided). Sample will be white.
d. Add one Nitrite No. 2 tablet and shake to disintegrate.
e. Continue adding the Nitrite No. 2 tablets one at a time until a pink
color persists for at least one minute.
Calculation:
Nitrite(ppm) = number of No. 2 tablets x 180
For example: If 9 tablets are used Nitrite = 9 x 180 = 1620 ppm.
f. Mark the result obtained on the log sheets provided against the
B. Chloride test
a. Take a 50 ml water sample in the container provided.
b. Add one Chloride tablet and shake to disintegrate; sample should
turn yellow if Chlorides are present.
c. Repeat tablet addition one at a time until the yellow colour
changes to orange/brown.
Calculation:
Chloride ppm = (number of tablets used x 20) 20
For example:
If 3 tablets are used, Chloride ppm = (3 x 20) 20 = 40 ppm
d. Mark the result obtained on the log sheets provided, against the
date on whichthe test was taken.
66
C. pH test
a. Dip one of the test strips into the water sample so that the colour
zone is completely immersed.
b. Compare the colour obtained with the reference, and read off the
printed pH value.
c. Mark the result obtained on the log sheet provided, against the
15.7 TEST RESULTS

15.7.1 Recording
The test results should be recorded on the Spectrapak 309 Rapid
Response log forms.
15.7.2 Reporting
Completed monthly log should be distributed as shown:
A. White copy Send to Unitor Rapid Response Centre.
B. Pink copy Vessels head office.
C. Yellow copy Retain for ships records.
15.7.3 Evaluation
A. Logs will be reviewed for adherence to specification requirements
by Unitors computerised RAPID RESPONSE system and staff.
B. A log review indicating the status of the system, problems and
recommendations will be issued to the ships operator.
15.8 DESCALING LOW SPEED MARINE DIESEL ENGINE

COOLING WATER SYSTEMS
Note: Be careful use protective glasses and gloves
Connect a thin (1/31/2) transparent hose to some low point of the system
and run it up to the level of the top of the expansion tank. You now have a
level indicator for the system.
Drain the system and fill up with clean tap water to the lowest level in the
expansion tank sight glass.
Connect the pressure side of the chemical cleaning module to the cooling
water inlet manifold. Make return connection from the bottom of the expansion tank to the mixing tank of the module.
The ships fresh cooling water pump should be isolated from the system
and not used for circulation, i.e. suction and pressure valves closed. The same
applies to auxiliary machinery such as evaporators, generators, etc. These
should be boiled out separately if necessary.
67
Sufficient Descalex to mix up a 510 % solution is gradually filled into the

mixing tank, well dissolved and fed into the inlet manifold.
Take a sample of the solution for later colour comparison.
The solution should be heated to 60 C using the engines cooling water
pre-heater.
Circulate the system for 1/2 hour, then close the shut-off valves on all
cylinders except one, and circulate for 15 minutes. Continue to circulate one
cylinder at a time for 15 minutes each, over a period of 4 to 6 hours, checking
the solution colour and temperature regularly. If the solution colour changes
from red to orange or yellow, indicating acid neutralisation, add sufficient
Descalex to the solution to return it to its original colour (usually 25 g per liter
of solution). This reinforcement of the solution should not be done more than
twice. If after two reinforcements the acid is still neutralised, the solution
should be drained off and the process started again with a fresh solution. This
will usually only be necessary when dealing with very thick deposits.
When the cleaning solution retains its red colour for one hour, the cleaning
operation may be considered complete and the solution can be drained off.
Fill up the engine with clean fresh water and circulate each cylinder for
ten minutes. Then drain each cylinder separately in order to get the highest
possible dumping speed.
Open all inspection covers and check that all debris that has formed during
descaling is flushed out. Close covers. Fill up the engine again and add 0.5 %
Alkalinity Control.
Circulate the solution to remove any remaining acidity and passivate steel
surfaces. Circulation must be maintained until sufficient level of pH value is
obtained. This should be tested through the whole engine. Drain the engine.
Adding the inhibitor DIESELGUARD NB ROCOR NB LIQUID.
Refill the engine with fresh water produced by the evaporator to the lowest
level in the expansion tank sight glass. Add sufficient cooling water treatment
for the initial dosage through the cleaning module.
Disconnect the cleaning module.
Put all valves in normal operating position and circulate the system with
the main cooling water pump for 15 minutes. Vent the system thoroughly
during this time.
Check the treatment concentration and adjust to 1500 ppm nitrite content.
Fill the expansion tank to the normal operating level using water from the
evaporator production.
Check the acid content of the system lubricating oil directly after the
descaling operation and repeat after 24 hours.
Virtually the same procedure as above can be followed when descaling
4 or 2 stroke trunk engines. However, this kind of engine seldom has shut-off
valves on the individual cylinders and therefore all cylinders must be
circulated simultaneously.
Medium-speed engines of this kind often have a drain bore Tell Tale Bore
68
from the space between the upper (water) and the lower (oil) cylinder liner
O-ring. This is to check for leakages.
The bores should be inspected when the engine is running. If leaks are
indicated, NO descaling should be performed unless the engine can be
dismantled and the cylinder liners pulled out immediately after the descaling
operation. Otherwise, you cannot be sure that all acid is flushed out/
neutralised, and corrosion of the sealing surface may occur.
15.9 DEGREASING MARINE DIESEL ENGINE

COOLING WATER SYSTEMS
When diesel engine cooling water systems become contaminated with oil and
and grease, the system should be cleaned to remove oily deposits, as they
can interfere with the cooling water corrosion treatment.
In Service Cleaning
This method may be undertaken with engine running at normal speed.
1) Take a 0.25 litre cooling water sample for future comparison and let it
stand in a clear glass container.
2) Calculate the amount of Tankleen Plus required for solution of 0.5 % i.e.
5 litres per 1000 litres cooling water. Drain off similar amount of cooling
water from engine if necessary. Slowly and intermittently add the cleaner
to the cooling system via either the expansion or return tank.
3) After 5 hours, take a 0.25 litre cooling water sample. This should be allowed
to stand in a clear glass container until any oil has risen to the top. The
progress of the cleaning operation can be gauged by comparing thickness
of this oil level with that of the first sample. A sample should be taken after
56 hours to monitor cleaning progress.
4) The cleaner can be left in the engine for a few days until a convenient port
is reached where the engine can be drained.
5) Drain off the complete engine cooling system and flush thoroughly with
clean water prior to re-filling with water of the required quality, to which
an appropriate anti-corrosion treatment such as Dieselguard NB or
Rocor NB Liquid should be added.
Out of service Cleaning
This method may be used when engine is stopped.
1) Take a 0.25 litre sample of cooling water for future comparison and allow it
to stand in a clear glass container.
2) Drain the cooling system and flush out with water then refill the system.
69
16 Reporting Analysis Results

3) Calculate the amount of cleaner required for a solution strength of 2 % i.e.
20 litres per 1000 litres cooling water. Drain of similar amount of cooling
water from engine if necessary. Add Tankleen Plus to the expansion tank
or return tank.
4) Circulate the solution through the system and heat until the water reaches
a temperature of about 60 C.
5) Continue circulation of the solution through the system for a minimum
of 5 hours.
6) Take a sample of cleaning solution from the system after a minimum
of 5 hours.
7) When cleaning is completed, drain off the cooling water system, and
thoroughly flush with clean water prior to refilling and adding an anticorrosion treatment such as Dieselguard NB or Rocor NB Liquid.
70
One important aspect of a good water treatment management system is to

ensure that analysis results and any action taken are recorded as the events
take place and the reports are properly maintained for future reference.
As mentioned earlier, special log forms are supplied separately for both
boiler water treatment and diesel engine cooling water treatment. These
should be completed by the water treatment officer responsible. Attention
should be paid not only to recording the results of various water analyses,
but to reporting any changes in circumstances that may have a direct or an
indirect influence on the results, including any major cleaning or repairs to
the system.
In order that Unitor may keep a watchful eye on water treatment programmes onboard individual vessels, it is essential that the instructions for
our Rapid Response programme are followed and logs sent promptly to our
Rapid Response Centre for review and comment.
Unitor will monitor the progress and performance of the onboard water
treatment programme and liaise with the vessels head office and ship
accordingly.
Examples of how to complete the report logs are given overleaf. Make sure
you use the correct log form in conjunction with your treatment programme.
Picture page 72, 73, 74, 75, and 76, shows log examples.
71
CHEMICALS
Unitor ASA
Chemical Business Unit

P.O. Box 300 Skyen
N-0212 Oslo
Norway
72
16 / REPORTING ANALYSIS RESULTS
73
CHEMICALS
CHEMICALS
Unitor ASA
Unitor ASA

P.O. Box 300 Skyen
N-0212 Oslo
Norway
74

P.O. Box 300 Skyen
N-0212 Oslo
Norway
75
CHEMICALS
Unitor ASA

P.O. Box 300 Skyen
N-0212 Oslo
Norway
17 Water Tests, Summary

17.1 SPECTRAPAK TEST KITS
309 Test Kit:
Nitrite
pH
Cl
310 Test Kit:
P-Alkalinity
Cl
pH
311 Test Kit:
P-Alkalinity
M-Alkalinity
PO4
Cl
pH
312 Test Kit:
Hydrazine/Sulphite
PC 22 Test Kit:
P-Alkalinity
M-Alkalinity
PO4
Cl
pH
Conductivity
Hardness
Ammonia
Hydrazine
Silica
Samples to be tested: Boiler water
Feed water
Condensate return
Make up water
Engine cooling water
17.2 TESTING
Boiler water:
76
P-Alkalinity
M-Alkalinity
Cl
PO4
pH
Hydrazine/Sulphite
Conductivity
Silica
Appearance
77
Feed water:
Cl
Conductivity
Make up water:
Cl
Hardness
Silica
Condensate return:
Cl
pH
Ammonia
Other actions in conjunction with previously mentioned:

Alkalinity
If P-Alkalinity test results are above limits even after not dosing chemicals,
check the P-Alkalinity of the make-up water.
Chlorides
If high Chloride readings exist after blowdown, check for sources of salt
water leaks:
A) Drain cooler
Engine cooling water: Nitrites

Chlorides
pH
Appearance
TEST DAILY
AS REQUIRED
TEST WEEKLY
EVERY FOUR DAYS
AS REQUIRED
Record all chemical tests on the Rapid Response logs.
17.3 TROUBLESHOOTING
78
Fault
Action
P-Alkalinity
Too high
Too low
Blowdown
Dose Alkalinity Control to the boiler
M-Alkalinity
Too high
Blowdown
Chlorides
Too high
Blowdown
pH
Too low
Too high
Dose Alkalinity Control to boiler

Blowdown
Phosphate
Too high
Too low
Blowdown
Dose Hardness Control
Hydrazine/Sulphite Too high

Too low
Blowdown
Check for source of Oxygen leakage
Increase chemical dosage
Conductivity
Blowdown
17 / WATER TESTS, SUMMARY
pH
Check pH of condensate. If too low, increase dosage of Condensate Control.
If too high, decrease dosage of Condensate Control.
Phosphate
If unable to maintain a Phosphate reading after dosing Hardness Control,
check the make-up water for Chlorides.
Hydrazine/Sulphite
Check temperature of feedwater. In most cases, the higher the temperature
of the feedwater, the lower the dosage of Oxygen Control or Sulphite.
Conductivity
If conductivity readings remain high after blowdown, check for:
17.3.1 Boiler water tests
Too high
C) Heat exchangers
Always check the Chlorides of the feedwater, condensate return and make-up
water when Chloride readings in the boiler continue to be above maximum
limits. If you have steam on deck, check the return lines.
Testing is mandatory to make sure the water treatment programmes are

effective.
BOILER WATER
FEED WATER
CONDENSATE
ENGINE COOLING WATER
MAKE-UP WATER
B) Condenser
A) Chloride levels/leaks
B) Condensate return
C) Phosphate level
17.3.2 Cooling water tests

Nitrites
Fault
Action
Too low
Dose Dieselguard NB
or Rocor NB Liquid.
Stop dosing of chemical until the
Nitrite level is back down below the
max. limit.
Too high
pH
Too low
Check for salt water leaks and

combustion gas leakage.
Chlorides
Too high
Check for leaks. Increase the

chemical dosage to bring the Nitrite
level close to the upper limit (2400 ppm).
79
Nitrite
If Nitrite readings remain low after dosing Dieselguard NB or Rocor NB
Liquid, you may have a bacteriological problem. The cooling water
should then be analysed with appropriate test dip slides which can be
ordered from Unitor. Unitor also has available an effective biocide called
MAR-71, which is specially developed for bacteriological problems.
pH
Increase chemical dosage. If Nitrite level is within recommended limits,
dose Alkalinity Control to increase the pH.
17.3.3 Sea water cooling treatment
To avoid fouling in sea water systems, Unitor has developed a very
effective Amine-based dispersant of marine growth such as Shellfish
Algae and micro-organisms in order to prevent the a.m. problem.
Because of its filming properties, the product also acts as a corrosion
inhibitor.
Bioguard can be used in both static and flowing systems such as
ballast tanks and looped cooling systems.
80
17 / WATER TESTS, SUMMARY
The diagram on the previous page shows the typical dosage layout.
This can be modified to suit a particular situation. Although the
product will gradually clean fouled systems, treatment should
preferably be started on a clean system.
Dosage for sea water cooling systems:
Dose 0.6 ltr Bioguard for every 100 m3 of seawater flowing through the
system per hour. The system throughput is to be determined either from
the rating of the pump(s) or from the system specifications. Treatment is
necessary in coastal waters and should commence three days before
entering these waters and continue for three days after leaving coastal
waters. The calculated dose should be given over a one-hour period
and repeated every 48 hours.
Dosage for static ballast tanks:
Dose one litre of Bioguard per 100 m3 of water prior to ballasting,
followed by a monthly dose of 2 litre per 100 m3.
NB! Bioguard should only be diluted with fresh water prior to dosing
if necessary.
81
18 Evaporator Treatment
THE FRESH WATER EVAPORATOR (OR GENERATOR)
There are two main types:
THE VACUUM or FLASH EVAPORATOR
and
THE STEAM HEATED EVAPORATOR
18.1 THE VACUUM EVAPORATOR

Vacuum is maintained in the evaporator, considerably reducing the boiling
point of the water.
The heat source used is the engine jacket water. The jacket water is
circulated through the lower section of the evaporator where the heating
section is. This heating section is a series of vertical tubes surrounded by the
heating water. Sea water is pumped into the vertical tubes from below to be
heated by the jacket water. The water vapour produced rises to the top of the
evaporator where it comes into contact with cooling tubes and condenses.
The condensate is then taken off for storage. The system is very efficient
when correctly set up, but there are several points to consider:
A. 3 percent of seawater is dissolved minerals.
B. Evaporators of this type have a tendency to allow the seawater to foam
and so salt is carried over with the distilled water.
The treatment is to be fed continuously. The evaporator vacuum will pull
the treatment in and it will enter the evaporator with the seawater.
Sufficient treatment should be mixed for 24 hours operation. Treatment is
essential to keep the evaporator operating efficiently for longer periods
of time. It works in the following ways:
a. Some of the dissolved solids may form scale and the treatment
will help prevent the solids from adhering to the heating surfaces and
keep these scale formers in solution.
b. The sludge will be conditioned to make extraction of the concentrated
sea water (brine) easier.
c. The foaming tendency of the brine will be suppressed by anti-foaming
agents.
Unitor treatment is: Vaptreat.
Average dosage: 0.3 l/10 tonnes of distillate produced.
This is calculated on a standard brine density of 1.038 kg/l.
82
18 / EVAPORATOR TREATMENT
83
FRESH WATER GENERATOR

Type AFGU 1-E-10/1-E-15
19 Marine Equipment
19.1 SOME COMMON MARINE EQUIPMENT
19.1.1 High Pressure Boilers > 30 bar
Babcox & Wilcox Combustion Engineering
Foster Wheeler IHI
19.1.2 Low Pressure Boilers < 30 bar
Sunrod Aalborg Cochran Osaka Kawasaki MHI
19.1.3 Slow Speed Diesel Enginees < 120 rpm
Mitsubishi Sulzer MAN B & W Gtavrken Fiat GMT
19.1.4 Medium Speed Diesel Engines 120900 rpm
Wartsila Sulzer Pielstick Enterprise MAN B & W
MaK Deutz Bergen Diesel Daihatsu
19.1.5 High Speed Diesel Engines > 900 rpm
Hitachi Yanmar EMD Cummins Caterpillar
19.1.6 Evaporators
Alfa-Laval Desalt Atlas (bought by Alfa-Laval) Nirex
Maxim Weir
84
18 / EVAPORATOR TREATMENT
85
Notes:
86
20 / NOTES
Notes:
87
Notes:
88
20 / NOTES

Water Treatment Handbook

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Water Treatment Handbook

Uploaded by

Copyright:

Available Formats

UNITOR

Mail: P.O. Box 300 Skyen, N-0212 Oslo, Norway

Unitor ASA, P.O. Box 300 Skyen, N-0212 Oslo, Norway

ID. NO. 08 173

COUNTRY OF ORIGIN: NORWAY

3 Problems of Boiler Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

WATER TREATMENT HANDBOOK

WATER TREATMENT HANDBOOK

1 Water Treatment Philosophy

Cooling Water Treatments:

WATER TREATMENT HANDBOOK

WATER TREATMENT HANDBOOK

TEMPORARY HARDNESS (Alkaline Hardness) is due to bicarbonates of

and at 90 C approx. 1.5 mg O2/l, and

at 100 C approx. 0.0. mg O2/l,

Ca(HCO3)2 is called Calcium Bicarbonate.

BOILER WATER TREATMENT FUNDAMENTALS

The concept of employing water, fresh or distilled, as a power generating

WATER TREATMENT HANDBOOK

as electrolytes in the untreated water, leading to galvanic and other types of

Cations will combine only with anions.

Oil contamination may occur through mechanical failure, for

WATER TREATMENT HANDBOOK

Magnesium Carbonate when the solubility of this salt is exceeded.

WATER TREATMENT HANDBOOK

2.2.9 Calcium Sulphate (CaSO4)

D. ALKALINITY RELATIONSHIP TABLE

2.2.10 Dissolved Gases

*This is the correct alkalinity relationship for boiler water

2.2.11 Acidity, Neutrality and Alkalinity

A. ALKALINITY. The presence of Alkalinity in a water sample may be

B. P ALKALINITY. Phenolphtalein (P) Alkalinity (pH values greater than

pH is a very important factor for determining whether a water has a corrosive

C. M ALKALINITY. Total Alkalinity or M Alkalinity (pH values greater

WATER TREATMENT HANDBOOK

3 Problems of Boiler Water

3.1.1 Pitting Corrosion

The most common problems are:

The corrosion processes can affect boilers in the following ways:

General wastage of a boiler tube.

3 / PROBLEMS OF BOILER WATER

3.1.2 Stress Corrosion

WATER TREATMENT HANDBOOK

3.1.3 Other Related Problems

Causes and Effects

3.1.4 Factors Affecting Corrosion

Metal oxides are more soluble as pH

Chloride and Sulphate can penetrate

Carbon Dioxide and H2S reduces pH and

Mud, sand, clay, etc. settle to form deposits,

Promote different corrosion cells.

High temperature increases corrosion.

High velocity promotes erosion/cavitation.

Copper ions plate out on steel surfaces

3 / PROBLEMS OF BOILER WATER

3. The condensate is polluted:

WATER TREATMENT HANDBOOK

Change in Conditions When

Carryover in superheaters can promote failure due to overheating.

The scale causes the fuel consumption to increase by approx. 18 percent.

Excess Fuel Consumption in %,

Sudden load changes

Curve of middle values. The differences in the test results can be