Water

Treatment
Handbook

ID. NO. 08 173 REV. NO. 00 LOBO 09.97 5K COUNTRY OF ORIIGIN: NORWAY

UNITOR ASA
Mail: P.O. Box 300 Skøyen, 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
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 Skøyen, 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 Unitor’s 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
Unitor’s Laboratories which provide the technical expertise required to
answer all questions in regard to marine chemical applications.
Unitor’s 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
today’s 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.
II WATER TREATMENT HANDBOOK
INDEX Page
INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IV
1 Water Treatment Philosophy and Overview . . . . . . . . . . . . . . . . . . . . . . . 5
2 Basic Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
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
WATER TREATMENT HANDBOOK III
 INTRODUCTION 1 Water Treatment Philosophy
This Product Applications Handbook has been designed to provide specific and Overview
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 vari- 1.1 TYPES OF WATER
ous products, including the application of individual chemical products to General
properly maintain Low Pressure, Medium Pressure and High Pressure Boilers, Water could generally be described as the most important of all chemical
Diesel Engine Cooling Systems and Evaporators. substances. Its chemical designation is H2O; the water molecule is composed
of 2 Hydrogen atoms and 1 Oxygen atom.
Single Function Treatment Products:
1. Hardness Control Natural water
2. Alkalinity Control Raw water is the description of the water to which we have daily access.
3. Oxygen Control (Hydrazine) We can obtain our water from:
4. Catalysed Sodium Sulphite (Powdered & Liquid)
1. The ocean
5. Condensate Control
2. Surface sources (e.g. from lakes)
6. Boiler Coagulant
3. Underground sources
Low Pressure Boilers, Water Treatments: The water will vary in composition.
1. Combitreat (powdered)
The natural water cycle may be as below:
2. Liquitreat
3. Condensate Control

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 atmo-
sphere, 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 WATER TREATMENT HANDBOOK WATER TREATMENT HANDBOOK 5

 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

at 100 °C approx. 0.0. mg O2/l, 2.1 BOILER WATER TREATMENT FUNDAMENTALS
The concept of employing water, fresh or distilled, as a power generating
so, the higher the temperature, the less O2 can dissolve in water.
source and heat exchange medium originated and was realised with the
CO2 (Carbon Dioxide) dissolves in water as follows: inception of the steam generator or boiler, and has been applied most
CO2 + H2O > H2CO3 successfully and beneficially in this manner ever since.
Water has the ability to transfer heat from one surface to another, thereby
H2CO3 is a very weak acid. In contact with CaCO3 (ordinary lime), it is reactive maintaining the system within the correct operational temperature range
and the lime dissolves as follows: while generating steam to carry out work. However, water can adversely
CaCO + H CO > Ca++ + 2HCO –
3 2 3 3
affect metal components under the operational conditions normally found in
steam boilers and other heat exchange devices. The extent of deterioration
Ca(HCO3)2 is called Calcium Bicarbonate.
depends on the specific characteristics of the water and the system in which
SO2 (Sulphur Dioxide) is an air pollutant which stems from flue gases, so there it is being used.
is usually a high atmospheric content of this gas around industrial areas. In order to counteract the detrimental properties normally attributed to
2SO2 + O2 + 2H2O > 2H2SO4 water and its contaminants (dissolved and suspended solids and dissolved
gases), special chemical treatment programmes have been devised.
H2SO4 is called Sulphuric Acid, and this acid also dissolves lime (CaCO3) Accepted water treatment processes and procedures are constantly being
as follows: upgraded and modernised, and new methods are being developed to
CaCO3 + H2SO4 > CaSO4 + H2O + CO2. complement and/or replace older ones. Unitor utilizes the most modern,
practical programmes for the marine operator.
CaSO4 is called Calcium Sulphate (gypsum). Although water from marine evaporators and boiler condensate return
In other words, the gases dissolved in the water will increase the leaching of systems is essentially “pure”, minute quantities of potentially harmful
the subsoil’s minerals, so that we may have solutions in water due to: salts and minerals can be carried by this composition and feedwater into
the boiler, where they will accrue, ultimately resulting in serious problems in
TOTAL HARDNESS the steam generating unit. In addition, the water can also contain dissolved
Temporary hardness Permanent hardness 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
Calcium Bicarbonate Calcium Sulphate present some of the same problems experienced with distilled water, but in
Ca (HCO3)2 CaSO4 addition, certain contaminants which are naturally present in fresh water can
Magnesium Bicarbonate Magnesium Chloride be extremely destructive in boiler systems if not dealt with promptly and effect-
Mg (HCO3)2 MgCl2 ively. Soluble salts such as Chloride, Sulphate and Carbonate are present

6 2 / BASIC CHEMISTRY WATER TREATMENT HANDBOOK 7

 as electrolytes in the untreated water, leading to galvanic and other types of Oil contamination may occur through mechanical failure, for
corrosion, depending on the conditions in the system. In addition, Sulphates example, faulty oil deflectors at turbine glands passing lubrication oil to
and Carbonates have the potential to form insoluble, adherent, insulating gland seal condensers and main condensers, etc., or undetected leaks
“hard water” scale deposits on heat exchanger surfaces. at tank heating coils.
Any oil film on internal heating surfaces is dangerous, drastically
impairing heat transfer. Oil films therefore cause overheating of tube
2.2 CONTRIBUTING ELEMENTS metal, resulting in possible tube blistering and failure.
WHICH AFFECT BOILER WATER TREATMENT If oil contamination is suspected, immediate action must be under-
Most dissolved mineral impurities in water are present in the form of ions. taken for its removal.
These ions contain an electrical charge which is either positive (cation) or The first corrective measure in cleaning up oil leakage is to find and
negative (anion). These ions can join together to form chemical compounds. stop the point of oil ingress into the system. Then, by using a Unitor
To know which ions will combine, we need to know their electrical charge. degreaser, a cleaning solution can be circulated throughout the boiler
Ions of concern to us include the following: system to remove the existing oil contamination. Complete details on
this cleaning operation are covered later in the handbook.
Positive Chemical Negative Chemical Boiler Coagulant can assist in removing trace amounts of oil
ions symbol ions symbol contamination. Consult your Unitor representative for more specific
Sodium Na+ Chloride Cl – recommendations.
Calcium Ca++ Bicarbonate HCO3
Magnesium Mg++ Carbonate CO3– – 2.2.3 Iron Oxides
Hydrogen H+ Hydroxide OH – 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
Cations will combine only with anions. condensate system. Often, Iron Oxide will be deposited and retard heat
transfer within a boiler tube, at times resulting in tube failure. This
An example of this combining of ions is the action between Calcium and
usually occurs in high heat transfer areas, i.e. screening tubes nearest
Carbonate. The chemical compound which forms is Calcium Carbonate.
to the flame.
Other impurities which will affect the boiler water treatment control
include Copper, Iron Oxides, oil and dissolved gases. When iron is not present in the raw feedwater, its presence in the
boiler indicates active corrosion within the boiler system itself.
2.2.1 Copper Rust, the reddish form, is fully oxidized. More often, in a boiler with
Copper is introduced into a system by corrosion of Copper piping and limited Oxygen, it is in the reduced or black form as Magnetite (Fe3O4).
Copper alloys. In boilers, the source of this corrosion could be dissolved Fe3O4 is magnetic and can be readily detected with a magnet. It is
gases in the boiler water or the excessive use of Hydrazine which will a passivated form of corrosion and its presence shows that proper
corrode Copper and Copper alloys, allowing Copper to be carried back control of the system is being maintained.
to the boiler.
Copper in the boiler displaces metal from the tube surfaces and 2.2.4 Magnesium Carbonate (MgCO3)
plates out on the tubes. This condition often occurs under existing scale Magnesium hardness in fresh water usually accounts for about one-
and sludge deposits, which is known as under deposit Copper corro- third of the total hardness. The remaining two thirds can normally be
sion. Copper deposits are a serious problem in high pressure boilers. attributed to calcium.
Waterside deposits may be submitted to Unitor for complete analysis Since Magnesium Carbonate is appreciably more soluble in water
and determination of the correct procedures to follow for cleaning. than Calcium Carbonate, it is seldom a major component in scale
deposits. This is due to the preferential precipitation of the Carbonate
2.2.2 Oil ion by Calcium as opposed to Magnesium which remains in solution
To prevent oil from entering condensate and feedwater systems, certain until all soluble Calcium is exhausted.
safety equipment is generally incorporated to detect, remove, and Once this point is reached, any free Carbonate remaining in solution
arrest such contamination. will combine with the Magnesium and begin precipitating out as

8 2 / BASIC CHEMISTRY WATER TREATMENT HANDBOOK 9

 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 precipi-
tates 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 silicate-
coated tanks.
Once formed, pure Silica scale is extremely difficult to remove. It
forms a tight adherent glass-like film on metal surfaces, thereby pre-
venting proper heat transfer. In addition, in steam-generating devices it
can carry over with the steam coating the after-boiler sections, particu-
larly 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 300–400 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, becom-
ing 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 con-
tinue 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 (under-
deposit corrosion).
WATER TREATMENT HANDBOOK 11
 2.2.9 Calcium Sulphate (CaSO4) D. ALKALINITY RELATIONSHIP TABLE
Although Calcium Sulphate is more soluble in water than Calcium Hydroxide Carbonate Bicarbonate
Carbonate, it can be just as troublesome when present in boiler and Alkalinity Alkalinity Alkalinity
cooling water systems. Calcium Sulphate, like Calcium Carbonate, but P Alkalinity 0 0 Equal to
unlike most salts, has an inverse temperature/solubility relationship in =0 total
water. As gypsum, the hydrated form in which Calcium Sulphate is nor- P Alkalinity 0 2 times M Alkalinity
mally present in fresh water, its solubility increases until a temperature less than P Alkalinity minus 2 times
1/2 M Alkalinity P Alkalinity
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 P Alkalinity 0 2 times 0
equal to P Alkalinity
1,246 ppm, and at 220 °C it falls to 40 ppm. Calcium Sulphate reacts at 1/2 M Alkalinity
high-temperature surfaces essentially in the same manner as Calcium
*P Alkalinity 2 times 2 times the 0
Carbonate and with the same effects and consequences. However, greater than P Alkalinity difference
whereas Calcium Carbonate deposits are relatively easy to remove 1/2 M Alkalinity minus between M
using a comprehensive acid cleaning procedure, Calcium Sulphate is M Alkalinity and P Alkalinity
essentially impervious to the effects of normal acid descaling methods P Alkalinity Equal to 0 0
and usually must be removed by mechanical means. equal to M Alkalinity
M Alkalinity
2.2.10 Dissolved Gases *This is the correct alkalinity relationship for boiler water
Gases such as Oxygen and Carbon Dioxide that are dissolved in distilled
or fresh water, will further contribute to the deterioration of the boiler pH
system. Dependent upon conditions in the system (e.g. temperature, The pH of a solution is a measurement of the concentration of active acid or
pressure and materials of construction), dissolved Oxygen can cause base (alkaline constituent) in a solution.
pitting corrosion of steel surfaces, while Carbon Dioxide lowers the pH, To give a precise definition, pH is the negative logarithm of the Hydrogen
leading to acid and galvanic corrosion. Carbon Dioxide has the added ion concentration.
disadvantage of forming insoluble carbonate scale deposits in an alka- A simpler explanation of pH is that it is a measure of relative acidity or alkal-
line environment when Calcium and Magnesium are present. inity 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
2.2.11 Acidity, Neutrality and Alkalinity or alkalinity.
All water can be classified into one of these categories. Acidity, A pH value of 7 indicates neutral. Below 7 indicates increasing acidity.
Neutrality and Alkalinity are only very general terms. We require more Above 7 up to 14 indicates increasing alkalinity.
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. 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 1 2 3 4 5 6 7 8 9 10 11 12 13 14
alkalinity of water.
B. P ALKALINITY. Phenolphtalein (P) Alkalinity (pH values greater than pH is a very important factor for determining whether a water has a corrosive
8.3) measures all the Hydroxide and one half of the Carbonate Alkalinity or scale-forming tendency.
which is sufficient for our purpose of control. Bicarbonates do not show Water with a low pH will give rise to corrosion of equipment.
in this test as they have a pH of less than 8.4.
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 WATER TREATMENT HANDBOOK 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 proce-
dures when the boiler is shut down for lengthy periods, and by inade-
quate 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.
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 fail-
ure 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.

General wastage of a boiler tube. Stress corrosion

14 3 / PROBLEMS OF BOILER WATER WATER TREATMENT HANDBOOK 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 irreg-
ular circulation through tubes in high temperature zones induce these
cycling stresses.
”Caustic cracking” results from the contact of water of concen-
trated caustic alkalinity and steel which has not been stress relieved,
e.g. in riveted seams. This form of cracking follows the grain bound-
aries. 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 con-
siderable 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 5–10 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 3. The condensate is polluted:

a. By heat exchanger leaks
1) pH Metal oxides are more soluble as pH
b. By lubrication oil
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.
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 circula-
tion 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.

16 3 / PROBLEMS OF BOILER WATER WATER TREATMENT HANDBOOK 17

 3.3 CARRYOVER
Illustration of Change in Conditions When Carryover is any contaminant that leaves the boiler with the steam.
Typical Conditions With a Layer of Scale of just 3 mm
a Clean Boiler Tube Thickness Exists
Carryover can be:

• Solid • Liquid • Vapour

Effects of carryover:
• Deposits in non-return valve • Deposits in superheaters
• Deposits in control valves • 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.

Causes of carryover:
Mechanical:
• Priming • Sudden load changes • Boiler design
The scale causes the fuel consumption to increase by approx. 18 percent. • Soot blowing • High water level
Stress will arise in the steel as a result of the insulating effect of the scale.
Chemical:
Foaming due to:
Excess Fuel Consumption in %, • High Chlorides • High TDS • High alkalinity
depending on Thickness of Scale • Suspended solids • Oil • Silica
Curve of middle values. The differences in the test results can be
explained by differences in the composition of scale (porous–hard).
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. Circum-
stances 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 preheater’s
coils if they are leaking are very common causes of priming.

18 3 / PROBLEMS OF BOILER WATER WATER TREATMENT HANDBOOK 19

 4 Types of Boiler
What is a boiler?
A boiler is a steel pressure vessel in which water under pressure is con-
verted 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
Typical packaged boiler. Packaged boilers include a pressure vessel, burner, all the controls, air
fans, and insulation. The boiler is tested at the manufacturer’s plant and shipped to the customer,
4.2 WATER TUBE BOILER 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) Burner
2) Combustion space
3) Convection section
4) Stack
5) Air fans
6) Controls and accessories

Typical Scotch Marine firetube boiler (courtesy of Orr & Sembower, Inc.).

20 4 / TYPES OF BOILER WATER TREATMENT HANDBOOK 21

 4.3 FIRETUBE BOILERS 4.5 HIGH TEMPERATURE WATER (HTW) HEATING SYSTEMS
Wet back designs In recent years, interest has been revived in high temperature hot water
Have a water wall at the back of the boiler in the area where combustion heating systems for institutional, industrial and commercial plants. By
gases reverse direction to enter tubes. increasing the temperature and pressure of the hot water and increasing the
size of the generators, some advantages are gained over the low pressure
Dry back designs steam heating systems previously used. In other cases, special forced
Refractory is used at the back, instead of a water wall. Internal maintenance circulation boilers have been designed, which consist of many rows of tubes
is simplified, but refractory replacement is expensive and overheating, without a steam drum. In another type, heat is supplied by steam from
gauging and cracking of tube ends at the entrance to return gas passages a standard type of boiler which heats the water in a direct contact heater.
often cause problems. 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 treat-
ment 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. Medium-sized watertube boilers may be classified according to three basic tube arrangements.

22 4 / TYPES OF BOILER WATER TREATMENT HANDBOOK 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 5.1 TYPICAL BOILER SETUP ON A MOTOR SHIP

Advantages: 5.1.1 The Boiler System
• Rapid heat transmission This does not just consist of a boiler. As indicated by the figure above, it
• Fast reaction to steam demand 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
• High efficiency
single treatment: the combined boiler water treatment.
• Safer than firetube boilers
The steam plant consists of the following:
Disadvantages:
Storage tank
• More control than firetube boilers
This tank will hold the make-up water to be supplied to the various
• Higher initial cost systems as they lose water through leaks and through evaporation.
• More complicated to operate 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 treat-
ments. 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 WATER TREATMENT HANDBOOK 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 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.
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.
26 5 / BOILER SYSTEMS
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.
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.
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.
WATER TREATMENT HANDBOOK 27
 6 Unitor Boiler Water 7 Combined Treatment for Low
Treatment Products Pressure Boiler Water
6.1 THE MAIN PURPOSE OF BOILER WATER TREATMENT IS 7.1 LIQUITREAT
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
B. To maintain the correct pH and alkalinity values in feedwater and
the necessary alkalinity, and scavenges dissolved Oxygen. Liquitreat should
boiler water.
be added when deemed necessary as shown by water analysis results.
C. To prevent corrosion, especially corrosion caused by Oxygen. 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
D. To prevent the formation of scale, among other things by through a special dosing line. When a dosing arrangement is utilized, the
conditioning the sludge. chemical must be flushed to remove any residual left in the dosage lines and
E. To avoid foaming. 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
6.2 UNITOR PRODUCTS conditions, complete changeover in the feed tank can take some time. It is
Combined Treatment necessary to know the details of the flow pattern in the boiler for proper
testing and dosing of the chemical treatment to take place.
1. Liquitreat When several boilers have a common feed tank, dosing should be carried
2. Combitreat 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
Single Function Treatment was dosed to the boiler water.
For further recommendations on product dosage and control limits, refer
1. Alkalinity Control to the product data sheet in the Marine Chemical’s Manual.
2. Hardness Control
7.2 COMBITREAT
3. Oxygen Control Combitreat is a combined product chemical treatment similar to Liquitreat but
4. Catalysed Sodium Sulphite in powder form without Oxygen scavenger, which precipitates hardness and
provides the boiler water with the necessary alkalinity.
5. Cat. Sulphite L Combitreat should be applied as a solution and added when deemed
necessary as shown by water analysis results. The recommended dosage
6. Boiler Coagulant
must be dissolved in warm water, 30–60 °C in a suitable steel or plastic
7. Condensate Control 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.
NOTE: In addition to our combined product chemicals, Condensate Control should be used in all boiler systems to
keep the Condensate pH level between 8.3–9.0. 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 WATER TREATMENT HANDBOOK 29

 8 Tests for Boiler Water,
Low Pressure
8.1 UNITOR’S LOW PRESSURE COMBINED BOILER WATER 8.4 pH
TREATMENT PROGRAMME Recommended limits of 9.5–11.0. An additional test to determine the pH of the
The tests recommended in order to maintain boiler water within the desired boiler water can be carried out to give a better overall understanding of the
level of quality when treating with Unitor Liquitreat/Combitreat are as follows: boiler water quality. This test is optional.
The pH of the boiler water should be maintained within the range of
A. P-Alkalinity – Recommended Limits: 100–300 ppm as CaCO3. 9.5–11.0 to prevent any corrosion attack on the boiler metal. pH values below
B. Chlorides – 200 ppm maximum as Cl. 9.5 indicate, a greater possibility of corrosion and in such a situation,
treatment levels should be increased accordingly to restore boiler water
C. Condensate pH – 8.3–9.0.
to optimum quality.
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 para-
8.5 CONDENSATE pH
meters is desirable to enable better interpretation and correct application To control corrosion in after boiler, condensate and feedwater sections, the
of treatment. To increase the condensate pH, use Unitor’s Condensate Control condensate pH should be kept between 8.3 and 9.0. Monitoring the pH of this
in conjunction with your combined product boiler water treatment. It is water is very important in being able to maintain a complete Boiler Water
recommended that you dose Condensate Control on a continuous basis, to Treatment Management Programme.
maintain the condensate pH within the recommended range of 8.3–9.0
at all times.
8.6 TESTING REQUIREMENTS
8.6.1 Low Pressure Boiler Water Treatments:
8.2 CONTROLLING ALKALINITY A. Unitor Combined Treatment Products
The alkalinity is a more accurate indicator of the boiler water condition than is a. Combitreat – For systems up to 17.5 bar.
the pH. The Phenolphtalein (P) alkalinity is measured to determine whether b. Liquitreat – For systems up to 30 bar.
the correct conditions of alkalinity exist in the boiler to:
B. Test Equipment – Unitor Spectrapak 310 Test Kit.
A. Provide a suitable environment for the precipitation of hardness salts as
desirable sludge materials. C. Specification Control Limits.
a. P-Alkalinity: 100–300 ppm (as CaCO3).
B. To help the formation of Magnetite (Fe3O4) in the presence of Oxygen b. Chloride: 200 ppm maximum.
scavengers (i.e. Hydrazine/Sulphite). c. Boiler Water pH: 9.5–11.0 (optional).
C. Maintain Silica in solution to prevent Silica scale formation. d. Condensate pH: 8.3–9.0.

D. Testing preparations and equipment.

8.3 CONTROLLING CHLORIDES a. Boiler Water Sample preparation: – Cool sample to 20–25 °C.
The Chloride value will reveal any presence of dissolved salts in the boiler. An – Filter as required.
increase, gradual or sudden, in the level of Chlorides is an indication of con- b. Sample Analysis: – Spectrapak 310 Test Kit
tamination by sea water, and Chlorides are often used as a reference point Reagents: – P-Alkalinity tablets – Chloride tablets.
when controlling rate of blowdown. Too high a Chloride level indicates that – pH strips with ranges 6.5–10.0 and 7.5–14.0.
undesirable amounts of salts are present, leading to possible foaming and/or – Equipment – 200 ml sample bottles.
scale and deposit formation. – Test procedures.

30 8 / TESTS FOR BOILER WATER/LOW PRESSURE WATER TREATMENT HANDBOOK 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.
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.
D. Mark the result obtained on the log sheets provided, against the
date at which the test was taken.
8.6.3 Chloride test
A. For boilers under 30 bar, take a 50 ml sample in the stoppered bottle
provided.
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, 7.5–14.0.
For Condensate water, 6.5–10.0.
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
date at which the test was taken.
32 8 / TESTS FOR BOILER WATER/LOW PRESSURE
It is essential that the condensate pH is maintained within 8.3–9.0. Test
this with Unitor’s 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)
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. Calculate as follows:
Sulphite content = Number of Sulphite No. 2 L.R. tablets x 10.
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.
8.7 TEST RESULTS – COMBINED TREATMENT
A. Recording – Always use Unitor’s 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 Unitor’s 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
Unitor’s Rapid Response staff.
2. A report letter indicating the status of the ship’s system, any
problems and relevant recommendations will be issued to the
ship’s operator.
WATER TREATMENT HANDBOOK 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 individu-
ally. 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.
9.1 HARDNESS CONTROL
Hardness Control is a Phosphate powder product used in boiler water treat-
ment 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 mini-
mises 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. There-
fore, 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.
9.2 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 9 / UNITOR COORDINATED TREATMENT PRODUCTS
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.
9.3 OXYGEN CONTROL (HYDRAZINE, N2H4)
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 conden-
sate, 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.
The reaction of Hydrazine in boilers
is therefore threefold:
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 recom-
mendations on product dosage and control limits, refer to the Marine
Chemicals Manual.
WATER TREATMENT HANDBOOK 35
 9.4 CATALYSED SODIUM SULPHITE (POWDER) AND CAT. 9.7 CHEMICAL INJECTION POINTS FOR LOW PRESSURE
SULPHITE L (LIQUID) Boiler systems
Unitor’s Catalysed Sulphite products are used as scavengers in place of The following diagram depicts a typical Low Pressure Boiler System. Note
Hydrazine where economy is of importance, or used in low pressure boilers injection point for chemicals; when dosing chemicals, the recommendation to
with open feed systems where feed inlet temperatures are low. Sulphite achieve the best possible results is to always dose all chemicals in the diluted
combined with Oxygen forms Sulphate, which adds solids to the boiler water. form on a continuous basis.
It should subsequently not be used in boilers at pressures above 30 bars
1 Dosage to hot well or feed tank. All chemicals can be dosed at these points.
where the TDS level is critical. Sulphite is also used as a substitute for
However, the recommended dosage of Alkalinity Control and Hardness
Hydrazine when rust and scale deposits are present in boiler systems on
Control is either no. 2 feed line or no. 3 chemical feed injection directly to
ships being returned to service. Hydrazine tends to remove Iron Oxide
the boiler. Oxygen Control and Sulphite should preferably be dosed to the
deposits present throughout the boiler system. An amine (Condensate Control)
feed tank on a continuous basis.
should be used in conjunction with Oxygen scavengers to maintain the
All combined products can be dosed into the hot well.
condensate pH within the desirable ranges throughout the entire condensate
and feedwater system. 2 Dose to injection no. 2 is required to the feed line by means of a pressure
For further recommendations on product dosage and control limits, refer to injector or dosage pump. Dosage should be continuous, however water can
the Marine Chemicals Manual. 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
9.5 CONDENSATE CONTROL
Hydrazine, Sulphite or Condensate Control is recommended on
Condensate Control is a neutralising volatile amine recommended for use a continuous basis in the condensate system.
in all boiler systems to raise the pH of condensate and steam to
a non-corrosive level (pH 8.3–9.0). 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 conden-
sate 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 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.
For further recommendations on product dosage and control limits, refer to
the Marine Chemicals Manual.

36 9 / UNITOR COORDINATED TREATMENT PRODUCTS WATER TREATMENT HANDBOOK 37

 10 Tests for Boiler Water,
Medium Pressure
(31–60 BAR)

In dosing medium pressure boilers, utilise Unitor’s Coordinated Boiler Water 10.3 TEST PROCEDURES
Treatment Management Programme. This includes Alkalinity Control, 10.3.1 Phosphate (ppm) PO4
Hardness Control, Oxygen Control, Condensate Control and Boiler Coagulant.
The following tests are recommended to maintain medium pressure boiler A. Take the comparator with the 10 ml cells provided.
water within the desired level of quality when utilising Unitor’s Coordinated B. Slide the Phosphate disc into the comparator.
BWT Programme are as follows:
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. P-Alkalinity: . . . 100–130 ppm CaCO3 E. To the other cell add one Phosphate tablet, crush and mix until
2. M-Alkalinity: . . Below 2 x P-Alkalinity completely dissolved.
3. Phosphate: . . . . 20–40 ppm as PO4
F. After 10 minutes, place this cell into the right-hand compartment
4. Hydrazine: . . . . 0.03–0.15 ppm as N2H4
of the comparator.
5. Chlorides: . . . . . <30 ppm
6. pH (boil. water): 9.5–11.0 G. Hold the comparator towards a light.
7. pH (condens.): . 8.3– 9.0
H. Rotate the disc until a colour match is obtained.
10.2 UTILISE UNITOR’S SPECTRAPAK 311/312*/SULPHITE TEST KIT I. Record the result obtained on the Spectrapak 311/312 log sheet
against the date on which the test was taken.
Reagents
A. Phosphate tablets
B. Chloride tablets
10.3.2 Chloride (ppm) Cl
C. P-Alkalinity tablets
The range of Chlorides to be tested determines the size of water sample
D. M-Alkalinity tablets
used. To save tablets, the use of a small water sample is recommended
E. pH papers (6.5–10.0 & 7.5–14.0)
when the Chloride level is expected to be high, i.e. for low Chloride
F. pH reagent
levels use 100 ml water sample, for higher Chloride levels use 50 ml
G. Filter paper
water sample. However, it should be noted that the accuracy of the test
H. Hydrazine reagent*
results increases with the size of the water sample.
I. Sulphite tablets*
Equipment A. Take the water sample in the stopper bottle provided.
A. 200 ml sample bottles B. Add one Chloride tablet and shake to disintegrate. Sample will turn
B. Lovibond 2000 comparator yellow if Chlorides are present.
C. Phosphate disc 3/70
D. 10 ml molded cells C. Repeat tablet addition, one at a time (giving time for the tablet
E. Hydrazine disc 3/126* to dissolve), until the yellow colour changes to permanent
F. Sulphite test tube* red/brown.
* Optional. Either the Hydrazine Test Kit (Spectrapak 312) or the Sulphite Test Kit must be utilised. D. Count the number of tablets used and perform the following
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. calculation:

38 10 / TESTS FOR BOILER WATER MEDIUM PRESSURE WATER TREATMENT HANDBOOK 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.
For 50 ml water sample: Chloride ppm = (Number of tablets x 20) –20
e.g. 4 tablets = (4 x 20) –20 = 60 ppm.
E. Record the result obtained on the log sheet provided, against the
date on which the test was taken.
10.3.3 P-Alkalinity (ppm) CaCo3
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.
G. Retain the sample for the M-Alkalinity test.
10.3.4 M-Alkalinity (PPM CaCO3)
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
D. Record the result on the log sheet provided, against the date on
which the test was taken.
10.3.5 pH Test
7.5–14.0 For boiler water
6.5–10.0 For condensate water
40 10 / TESTS FOR BOILER WATER MEDIUM PRESSURE
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 the strip from the sample and compare the colour
obtained with the colour scale on the pH indicator strips container.
E. Record the pH value result on the log sheet provided, against the
date at 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. Hold up to the light and rotate the disc until a colour match
is obtained.
H. Record the reading shown as ppm Hydrazine.
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. 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.
10.3.8 Test results – Coordinated treatment
A. Recording – Always use Unitor’s Rapid Response log forms to
record all readings and to keep track of all results.
WATER TREATMENT HANDBOOK 41

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 Unitor’s 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 rewied at the Unitor Rapid Response Centre for
adherence to recommended specifications, with the aid of
Unitor’s computerized Rapid Response programme and staff.
2. A report letter indicating the status of the ship’s system, any
problems and relevant recommendations will be issued to the
ship’s operator.
42 10 / TESTS FOR BOILER WATER MEDIUM PRESSURE
11 High Pressure
Boiler Water Control
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.
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 tempera-
tures 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
WATER TREATMENT HANDBOOK 43
 levels in the condensate. Of course, precise control and dosage of Hydrazine SPECTRAPAK TEST UNITOR TREATMENT
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 Water to be Spectrapak Control Unitor
react with the trace amounts of Oxygen left in your feedwater after analysed water analysis limits treatment
deaeration. Unitor recommends a 0.05 ppm residual of Hydrazine in your boiler products
water. However, theoretically, any test results above 0.03 ppm will indicate
the presence of Hydrazine and this is an adequate residual to assure Oxygen- Feedwater Hardness 0
free boiler water. Oxygen (optional) < 10 ppb Oxygen Control
Controlling the pH and Phosphate coordination of the boiler water is also Chlorides < 5 ppm –
very critical. The coordination of the dosage of these products will prove to
maintain your internal boiler surfaces free from caustic embrittlement Boiler water P-Alkalinity Reference Alkalinity Control
corrosion and deposition. M-Alkalinity Reference Alkalinity Control
Unitor’s high pressure coordinated pH-Phosphate boiler water treatment pH (coordinate) 9.6–10.2 Alkalinity Control
programme is designed to maintain your boilers in optimum condition. If you Phosphate (coordinate) 10–25 ppm Hardness Control
experience any difficulties in controlling the programme prescribed herein, Hydrazine 0.05–0.10 ppm Oxygen Control
contact your local Unitor representative. Chlorides < 20 ppm –
Lastly, a routine for set periodic blowdown will enhance the results of this Silica < 3 ppm –
boiler water treatment programme. Even if test results are within good range Cond. < 300 µS/cm –
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 Condensate pH 8.3–9.0 Condensate
will fit into the vessel’s normal operating procedures to allow a complete Control
blowdown procedure, including a bottom blow and a blow of each header Chlorides < 5 ppm –
and to remove the sludge build-up. Unitor recommends that this routine be Ammonia < 0.3 ppm –
performed twice a day. Of course, if conditions warrant it, additional blows
should be performed.
11.3 TESTING HP – BOILER WATER TEST KIT PC 22 PHOTOMETER
PC 22 LED filter photometers are micro-processor controlled and have been
specially designed for this purpose. Production using the most modern SMD
11.2 TREATMENT PROGRAMME FOR BOILERS OPERATING technology, ergonomically-styled housing and the robust character of the
IN THE RANGE OF 60–83 BAR instruments guarantees high precision in analysing in laboratories as well as
using the instruments in the field.
Unitor recommeds the use of coordinated Phosphate/pH water The four-line display enables the clear indication of the complete date
treatment control. setting and an exemplary user’s direction.

The following high pressure boiler programme is based on the pressures,
temperatures and operating conditions of boilers operating in the range of
60–83 bar. Maintaining the chemical concentrations and parameters
prescribed will protect your boiler system. The following are specific control
parameters and products required.
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.

44 11 / HIGH PRESSURE BOILER WATER CONTROL WATER TREATMENT HANDBOOK 45

 Delivery Contents of SPEKTRAPACK PC 22 condensate water. High pressure boiler water using the
1 Ph-meter Reagents co-ordinated Phosphate-pH control method should always be
1 PC 22 Photometer in a case Ammonia tested using the pH meter for accuracy and the best results.
1 9 V-Battery Silica Note: Never touch the pH electrode sensor. Always rinse the
1 12 V-Mains adapter P-Alk sensor in untreated distilled water after use and keep the sensor
4 Cells M-Alk damp. Store in distilled water.
1 Conductivity meter Hardness To use, follow the manufacturer’s instructions provided with the
4 Stoppers Phosphate instrument. Calibration and slope adjustment can be checked using
1 Measuring cylinder 100 ml Hydrazine pH 7 and pH 10 buffers.
1 Test tube brush Chloride G. Conductivity Meter.
1 Stirring rod Note: Existing pH and conductivity meters can be used if onboard.
1 Cleaning kit Also verify test reults by standard solutions, pH buffer solutions or
1 Manual laboratory verification.
1 Guarantee-Certificate H. Ammonia.
I. Hardness.
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 J. Dissolved Oxygen (optional). Testing feed water for dissolved
similar equipment in a lab. Oxygen entering the boiler may be conveniently analyzed by insert-
(Unitor recommends using the Chemetrics dissolved Oxygen test. Consult ing Oxygen ampoule into a flowing stream of the sample. Feedwater
the Unitor office to arrange availability.) should be allowed to flush from sample line for a minimum of
10 minutes before taking sample. When the ampoule tip is snapped,
11.3.1 Spares vacuum inside the ampoule pulls the sample in where it mixes with
Standard spares are available from your local Unitor Marine Chemical the pre-measured reagent inside. A deep reddish/violet
representative. Order all spares from the on-going supply list provided colour forms proportional in intensity to the dissolved Oxygen
with these test instructions. A Replacement Tablet Reagent Pack. content of the sample. After inverting the ampoule several times to
Estimate 3-monthly requirements. mix the contents, compare that colour with the liquid colour
standards in the kit to determine the concentration of Oxygen.
11.3.2 Safety K. Silica.
Reagents are for chemical testing only; not to be taken internally. Keep
L. Boiler pH.
away from children. Wash hands after use.
M. Condensate pH.
11.3.3 High Pressure Procedures
A. Phosphate.
11.4 TEST RESULTS – HIGH PRESSURE BOILER WATER TREATMENT
B. P-Alkalinity.
11.4.1 Recording
C. M-Alkalinity. Always use Unitor’s Rapid Response log forms to record all readings
D. Chloride (Boiler and Condensate Water). and to keep track of all results.
E. Hydrazine. A. Log form – Ultra High Pressure Boiler Water Treatment Log, no. 314.
This test should not be performed at a temperature above 21 °C. B. Frequency – Samples should be drawn, tested and results logged at
A cooling coil should be fitted at the sampling point or the sample least once per day.
should be cooled immediately under running water. Cloudy samples
should be filtered before testing. 11.4.2 Reporting
F. pH (Boiler and Condensate Water). The electronic pH meter is the The completed log sheet for the month should be distributed as shown
most accurate and reliable method of testing high purity boiler and at the bottom of the form, at the end of each month:

46 11 / HIGH PRESSURE BOILER WATER CONTROL WATER TREATMENT HANDBOOK 47

 A. White copy – to Unitor’s Rapid Response Center in Norway 11.5.2 Coordinated phosphate/pH treatment system
(address labels at back of log pad)
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 ship’s system; any
problems and relevant recommendations will be issued to the
ship’s 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 If a pump and tank set is not available, Hydrazine (and Condensate
normal boiler Hydrazine residual due to oxides. This is normal, and until Control) can be added to the system through a tank and flowmeter into
a Hydrazine residual is obtained in the boiler water, test the feedwater the atmospheric drain tank, with injection point well below the water
for the Hydrazine content. Maintain the Hydrazine reading in the feed- level of the tank.
water between 0.02 and 0.03 ppm. No Oxygen is entering the boiler with Most boiler treatments use Sodium Hydroxide to produce the
the feedwater when Hydrazine is present in the water. However, required alkalinity in the boiler water. This procedure is often called
be certain not to exceed the max. level of 0.1 ppm in boiler water. “The Free Caustic Regime”, which means that if a sample of the boiler
Hydrazine may be dosed into the feed pump suction, or preferably, water were evaporated to dryness in an inert atmosphere, the remain-
to the storage section of the de-aerator, which will maximize the ing solids would contain Sodium Hydroxide.
residence and reaction time of Oxygen control. High concentrations of Sodium Hydroxide can cause inter-crys-
A separate dosing tank and pump set should be used for dosing talline cracking and, in high pressure boilers operating with a high heat
Hydrazine to the system. (Condensate Control may be fed with the flux, caustic gouging can occur. Caustic gouging is a reaction between
Hydrazine.) Sodium Hydroxide and iron to form Sodium Ferrate. Nascent Hydrogen
The estimated daily dose should be mixed with condensate and the is liberated by this reaction and can cause Hydrogen embrittlement of
pump should be set to deliver the daily dosage over an entire the steel; often the embrittlement occurs simultaneously with the loss
24-hour period. of boiler metal due to gouging. To prevent this from occurring, a coordi-

48 11 / HIGH PRESSURE BOILER WATER CONTROL WATER TREATMENT HANDBOOK 49

 nated phosphate to pH ratio method is used to produce the alkalinity 11.6.3 Oxygen control – Dosage guide
required to protect the boiler steel from corrosion. Hydrazine test results Oxygen control Adjustment
The method of control, in practice, is to determine the pH of the Less than 0.05 ppm Increase dosage 25 %
boiler water and the Phosphate ppm level. These figures are then 0.05–0.10 ppm Maintain dosage more than
checked against the graph. If the intersection of Phosphate/pH values 0.10 ppm Decrease dosage 25 %
falls within the parallelogram zone or below the curve, no free Sodium
Hydroxide will be present, which is the desired situation. Note: Bear in mind that variations in plant loads and the efficiency
of the de-areateor will affect the actual dosage of Hydrazine.
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, 11.6.4 Condensate control – Dosage chart
add Alkalinity Control. If the Phosphate reading is below the recom- Litres per 10 tonnes Boiler Water Capacity
mended limits, add Hardness Control only. This procedure will also
Condens. pH Less than 8.3 8.3–9.0 over 9.0
reduce the pH. If the Phosphate reading is high, blow down to the
Dosage Increase by 25 % Maintain daily Reduce by 25 % every
correct level. The correct balance of Phosphate to pH, to eliminate free
ltr/day every 72 hours dose 0.75 ltr 72 hours
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. 11.6.5 Initial dosage for each ton capacity boiler water
NOTE: Balance of Phosphate/pH to eliminate free caustic is easily achieved with the use of HARDNESS CONTROL 23 gr/tonne
distilled (evaporated) feedwater. If raw or contaminated water is employed, it may
be difficult or impossible to achieve a proper balance.
ALKALINITY CONTROL 180 ml/tonne
OXYGEN CONTROL 120 ml/tonne
11.6 UNITOR TREATMENT CHEMICALS – DOSAGE GUIDES CONDENSATE CONTROL 0.75 ltr/day
11.6.1 Hardness Control – Dosage Guide 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.
Phosphate test Hardness control
Result ppm gr/ton Water treatment on-going supply list – 6 months estimate
0– 5 20.77
5–10 16
10–15 11 11.7 RECOMMENDED DOSAGE POINTS FOR MEDIUM PRESSURE
15–20 No Dose AND HIGH PRESSURE CONDENSATE AND
20–25 No Dose FEEDWATER SYSTEMS
25 and above Blow down 11.7.1 Hydrazine
Continuous to the storage section of the de-aerator.
11.6.2 Alkalinity Control – Dosage Guide
pH test Alkalinity control
result ppm ml/tonne 11.7.2 Condensate Control
Should be dosed to the condensate system on a continuous basis.
8.4 18
8.6 17 Note: The testing point for Condensate pH should be up-stream (before) from the dosage
point of Condensate Control.
8.8 17
9.0 16
9.2 16 For steam vessels, separate dosages of Oxygen Control and
9.4 15 Condensate Control are recommended for better individual control of
9.6 13 each chemical. However, if only one dosing unit is available, both
9.8–10.2 Satisfactory Oxygen Control and Condensate Control can be dosed together.
10.3 and above Blow down Hydrazine and Condensate Control are compatible with each other.

50 11 / HIGH PRESSURE BOILER WATER CONTROL WATER TREATMENT HANDBOOK 51


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.
12 Boiler Wet Layup
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 2–3 days before the layup date
1 Test the boiler treatment levels and blow down the boiler at regular inter-
vals 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.
150–200 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 “head”of 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 manufacturer’s 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 11 / HIGH PRESSURE BOILER WATER CONTROL WATER TREATMENT HANDBOOK 53

 13 Boiler Blowdown
Blowdown is the mechanical process employed to remove and lower The Chloride residue is used as a reference value for the TDS level, and is
excessive concentrations of dissolved and suspended solids in boiler water. used to determine blowdown requirements. An upper Chloride concentration
This procedure must be exercised on a regular basis to prevent solids from limit is prescribed for the system being monitored.
building up which in turn can result in steam carryover leading to contamina-
tion of the after-boiler system. In addition, the consequential concentration Blowdown as percent is expressed as:
and accumulation of sludge and scale in the boiler can cause heavy deposits
to collect on heat exchange surfaces. Once formed, these deposits reduce Cl in feedwater x 100
= % Blowdown
heat transfer and restrict water circulation, causing the boiler to operate at Cl in boiler.
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
A bottom blowdown may be done to rapidly remove high solids content in
temperature on the furnace-side of the boiler. This in turn can cause
the boiler water. Continuous or intermittent surface blowdown may be used to
overheating and tube failure.
achieve controlled reduction of TDS. The method used is usually dictated by
In general, most feedwater and makeup water is processed and monitored
the severity of the contamination and the conditions of the specific system
prior to entering the boiler to ensure that the concentrations of naturally-
involved. Observe all manufacturers’ recommendations for blowdown
occuring solids are at a minimum. If done properly, only small amounts of
procedures as improper procedures can be detrimental to the boiler.
these contaminants are allowed to get through. These, however, will
Therefore, the process used must be implemented and performed
concentrate in the system and therefore must be dealt with by the addition
judiciously, bearing in mind all parameters of the system (i.e. available
of water treatment chemicals.
makeup water, available chemicals, boiler load requirements, etc.).
Solids concentrations in boiler water are usually determined by
a conductivity meter which displays a visual readout of the ability of the EXCESSIVE BLOWDOWN WASTES WATER, HEAT & CHEMICALS.
boiler water to transmit an electrical current. This characteristic, called
the specific conductance, is directly related to the solids content of the Dumping the Boiler
solution being measured. The greater the solids concentration, the higher Occasionally it may be necessary to remove the entire contents of the water-
the reading. The scale on the meter usually measures the results in units side of the boiler system, or to prepare the unit for dry layup when it is to be
of electrical conductance as either siemens or microohms per centimeter decommisioned for an extended period of time. The boiler must never be
at 25 °C. This value can be multiplied by a specific factor to determine emptied while the system is still hot, as this can cause solids to bake onto the
the dissolved solids concentration. Some meters have scales that read hot surfaces, forming deposits which are extremely difficult to remove. Since
directly in parts per million of total dissolved solids. Thus, these devices the boiler internals retain heat for a considerable period of time after the
are called both conductivity and TDS meters. In some systems, these system is taken off line, a wait of at least twenty-four hours is recommended
meters are permanently installed to continuously monitor boiler, from when the unit is shut down before commencing the dumping process.
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 WATER TREATMENT HANDBOOK 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 pre-
liminary investigation and/or lab analysis are known, the appropriate cleaning
procedure or procedures can be determined and implemented as follows.
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 originally-
detemined cleaning pressure.
56 14 / CHEMICAL CLEANING OF BOILERS
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.
14.2 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 approxi-
mate 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 conta-
mination as follows. Ensure all boiler internals needed to be cleaned.
Degree of % by Volume of
Contamination Tankleen Plus in Water
Light 1–2 %
Moderate 2–3 %
Heavy* 3–5 %
* If contamination is particularly heavy, Tankleen Plus can be substituted
by Carbon Remover at the rate of about 10 % by volume.
WATER TREATMENT HANDBOOK 57
 D. If circulation pump is being used, start circulating solution. Fire the
boiler for about 5 minutes, then secure for 15–20 minutes. Continue
this process until the water temperature reaches 50–60 °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 2–4 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
A. Inspect boiler interior as thoroughly as possible to determine degree of information.
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 Unitor’s 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 Descaling Liquid Descalex

Contamination in Water in Water
Light 5–10% 3–5%
Moderate 10–15% 5–10%
Heavy 15–20% 10–15%

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 4–12 hours depending upon the degree of contamination.

58 14 / CHEMICAL CLEANING OF BOILERS WATER TREATMENT HANDBOOK 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. Exceeding the solubility of the compound in water.
B. Formation of small nuclear particles.
C. Adequate contact time for crystal growth.
D. 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.
WATER TREATMENT HANDBOOK 61
 The steam heater is used to warm the engine up from cold. An air – The chart below can be used to determine the dosage requirement
separator is normally installed to get rid of entrained air in the system. necessary to achieve a nitrite residual level between the minimum
The water added to the expansion tank is termed “make-up” water. and maximum specification range limits.
Distilled water shall preferably be used for these cooling systems.
This is normally made onboard by a fresh water evaporator (or Nitrite (as ppm NO2) 0 180 360 540 720 900 1080 1260 1440 1620–2400
generator). A useful way of increasing the plant efficiency is to utilise Dieselguard NB Kg/1000 L 2.88 2.52 2.16 1.80 1.44 1.08 0.72 0.36 0 0
the heat taken from the engine to provide a heat source to the
evaporator. 15.3.3 Rocor NB liquid dosage chart
If evaporated water cannot be used for make-up, then fresh shore Unitor Rocor NB Liquid
water will have to be used. This is normally much higher in impurities. A. Initial dosage for an untreated system is 9 litres/1,000 litres of
The engine water temperature is in the region of 65 °C to 75 °C at the distilled water. This will bring the treatment level up to a minimum
inlet to the engine. It is maintained at this temperature by controlling level of 1000 ppm.
the cooling. The cooler is bypassed if the temperature drops.
B. The chart below can be used to determine the dosage require-
15.2.2 Corrosion ment necessary to achieve a Nitrite residual level between the
As mentioned above, this is the main problem in diesel engine cooling minimum and maximum specification range limits.
systems. The water contains some Oxygen, and if it is untreated, an
Nitrite (as ppm NO2) 0 180 360 540 720 900 1080 1260 1440–2400
ideal environment will exist for all types of corrosion.
Rocor NB Liquid L/1000 L 13.0 11.3 9.7 8.1 6.5 4.9 3.3 1.7 0

Note: When initially dosing a cooling water system, it is typical that the initial dosage may
15.3 DIESELGUARD NB AND ROCOR NB LIQUID vary from vessel to vessel, or system to system.Total passivation of the cooling
15.3.1 How do they work? water system will consume more product than when making Nitrite up as mainte-
nance dosages. The quality of make-up water will also affect initial dosage rates.
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 treat-
ment 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.

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 15 / DIESEL ENGINE COOLING WATER TREATMENT WATER TREATMENT HANDBOOK 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 1000–2400 ppm as NO2
2. pH 8.3–10.0
3. Chlorides 50 ppm maximum
15.4.1 Nitrite – Recommended Limits 1000–2400 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.
15.4.2 pH – Recommended Limits 8.3–10
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 Unitor’s 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.
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 manu-
facturer 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 15 / DIESEL ENGINE COOLING WATER TREATMENT
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 representa-
tive 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:
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
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.
WATER TREATMENT HANDBOOK 65
 15.6 TEST EQUIPMENT – UNITOR SPECTRAPAK 309 C. pH test
TEST KIT TEST PROCEDURES a. Dip one of the test strips into the water sample so that the colour
15.6.1 Sample preparation: zone is completely immersed.
A. Cool sample to 21–25 °C b. Compare the colour obtained with the reference, and read off the
B. Filter if necessary to clarify. printed pH value.
c. Mark the result obtained on the log sheet provided, against the
15.6.2 Spectrapak 309 content: date on which the test was taken.
A. Reagents:
a. Nitrite No. 1 tablets 15.7 TEST RESULTS
b. Nitrite No. 2 tablets
c. Chloride tablets 15.7.1 Recording
d. pH test strips (6.5–10.0) The test results should be recorded on the Spectrapak 309 Rapid
Response log forms.
B. Equipment:
a. Syringe 15.7.2 Reporting
b. Plastic sample container Completed monthly log should be distributed as shown:
15.6.3 Test methods: A. White copy – Send to Unitor Rapid Response Centre.
A. Nitrite test
a. Take a 5 ml water sample with the syringe and put into the B. Pink copy – Vessel’s head office.
container provided. C. Yellow copy – Retain for ship’s records.
b. Make the sample up to 50 ml using distilled water.
c. Add two Nitrite No. 1 tablets and shake to disintegrate (or crush 15.7.3 Evaluation
with the rod provided). Sample will be white.
d. Add one Nitrite No. 2 tablet and shake to disintegrate. A. Logs will be reviewed for adherence to specification requirements
e. Continue adding the Nitrite No. 2 tablets one at a time until a pink by Unitor’s computerised RAPID RESPONSE system and staff.
color persists for at least one minute.
B. A log review indicating the status of the system, problems and
Calculation: recommendations will be issued to the ship’s operator.
Nitrite(ppm) = number of No. 2 tablets x 180
For example: If 9 tablets are used Nitrite = 9 x 180 = 1620 ppm. 15.8 DESCALING LOW SPEED MARINE DIESEL ENGINE
f. Mark the result obtained on the log sheets provided against the COOLING WATER SYSTEMS
date on which the test was taken.
Note: Be careful – use protective glasses and gloves
B. Chloride test Connect a thin (1/3”–1/2”) transparent hose to some low point of the system
a. Take a 50 ml water sample in the container provided. and run it up to the level of the top of the expansion tank. You now have a
b. Add one Chloride tablet and shake to disintegrate; sample should level indicator for the system.
turn yellow if Chlorides are present. Drain the system and fill up with clean tap water to the lowest level in the
c. Repeat tablet addition one at a time until the yellow colour expansion tank sight glass.
changes to orange/brown. Connect the pressure side of the chemical cleaning module to the cooling
Calculation: water inlet manifold. Make return connection from the bottom of the expan-
Chloride ppm = (number of tablets used x 20) –20 sion tank to the mixing tank of the module.
For example: The ship’s fresh cooling water pump should be isolated from the system
If 3 tablets are used, Chloride ppm = (3 x 20) –20 = 40 ppm and not used for circulation, i.e. suction and pressure valves closed. The same
d. Mark the result obtained on the log sheets provided, against the applies to auxiliary machinery such as evaporators, generators, etc. These
date on whichthe test was taken. should be boiled out separately if necessary.

66 15 / DIESEL ENGINE COOLING WATER TREATMENT WATER TREATMENT HANDBOOK 67

 Sufficient Descalex to mix up a 5–10 % 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 engine’s 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 15 / DIESEL ENGINE COOLING WATER TREATMENT
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
5–6 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.
WATER TREATMENT HANDBOOK 69

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 anti-
corrosion treatment such as Dieselguard NB or Rocor NB Liquid.
70 15 / DIESEL ENGINE COOLING WATER TREATMENT
16 Reporting Analysis Results
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 pro-
grammes 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 vessel’s 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.
WATER TREATMENT HANDBOOK 71
 CHEMICALS
Unitor ASA
Chemical Business Unit
P.O. Box 300 Skøyen
N-0212 Oslo
Norway

72 16 / REPORTING ANALYSIS RESULTS WATER TREATMENT HANDBOOK 73

 CHEMICALS CHEMICALS

Unitor ASA Unitor ASA

Chemical Business Unit Chemical Business Unit
P.O. Box 300 Skøyen P.O. Box 300 Skøyen
N-0212 Oslo N-0212 Oslo
Norway Norway

74 16 / REPORTING ANALYSIS RESULTS WATER TREATMENT HANDBOOK 75

 17 Water Tests, Summary

Norway
N-0212 Oslo
P.O. Box 300 Skøyen
Chemical Business Unit
Unitor ASA
CHEMICALS
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: – P-Alkalinity
– M-Alkalinity
– Cl
– PO4
– pH
– Hydrazine/Sulphite
– Conductivity
– Silica
– Appearance

76 16 / REPORTING ANALYSIS RESULTS WATER TREATMENT HANDBOOK 77

 Feed water: – Cl Other actions in conjunction with previously mentioned:
– Conductivity
Alkalinity
Make up water: – Cl If P-Alkalinity test results are above limits even after not dosing chemicals,
– Hardness check the P-Alkalinity of the make-up water.
– Silica
Chlorides
Condensate return: – Cl If high Chloride readings exist after blowdown, check for sources of salt
– pH water leaks:
– Ammonia
A) Drain cooler B) Condenser C) Heat exchangers
Engine cooling water: – Nitrites
– Chlorides Always check the Chlorides of the feedwater, condensate return and make-up
– pH water when Chloride readings in the boiler continue to be above maximum
– Appearance limits. If you have steam on deck, check the return lines.

Testing is mandatory to make sure the water treatment programmes are pH

effective. Check pH of condensate. If too low, increase dosage of Condensate Control.
If too high, decrease dosage of Condensate Control.
BOILER WATER – TEST DAILY
FEED WATER – AS REQUIRED Phosphate
CONDENSATE – TEST WEEKLY If unable to maintain a Phosphate reading after dosing Hardness Control,
ENGINE COOLING WATER – EVERY FOUR DAYS check the make-up water for Chlorides.
MAKE-UP WATER – AS REQUIRED
Hydrazine/Sulphite
Record all chemical tests on the Rapid Response logs. Check temperature of feedwater. In most cases, the higher the temperature
of the feedwater, the lower the dosage of Oxygen Control or Sulphite.
17.3 TROUBLESHOOTING Conductivity
17.3.1 Boiler water tests If conductivity readings remain high after blowdown, check for:
Fault Action A) Chloride levels/leaks B) Condensate return C) Phosphate level
P-Alkalinity Too high Blowdown
Too low Dose Alkalinity Control to the boiler 17.3.2 Cooling water tests
M-Alkalinity Too high Blowdown Fault Action
Chlorides Too high Blowdown Nitrites Too low Dose Dieselguard NB
or Rocor NB Liquid.
pH Too low Dose Alkalinity Control to boiler
Too high Stop dosing of chemical until the
Too high Blowdown
Nitrite level is back down below the
Phosphate Too high Blowdown max. limit.
Too low Dose Hardness Control
pH Too low Check for salt water leaks and
Hydrazine/Sulphite Too high Blowdown combustion gas leakage.
Too low Check for source of Oxygen leakage
Increase chemical dosage Chlorides Too high Check for leaks. Increase the
chemical dosage to bring the Nitrite
Conductivity Too high Blowdown level close to the upper limit (2400 ppm).

78 17 / WATER TESTS, SUMMARY WATER TREATMENT HANDBOOK 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.
WATER TREATMENT HANDBOOK 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 WATER TREATMENT HANDBOOK 83

 FRESH WATER GENERATOR
19 Marine Equipment
Type AFGU 1-E-10/1-E-15
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 • Gøtaværken • Fiat GMT

19.1.4 Medium Speed Diesel Engines 120–900 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 WATER TREATMENT HANDBOOK 85

 Notes: Notes:

86 20 / NOTES WATER TREATMENT HANDBOOK 87

 Notes:

88 20 / NOTES