Guideline

Guidelines
Giudelines for Feed
Water, Boiler Water
and Steam Quality
for Power Plants /
VGB-R 450 Le
Industrial Plants
Second Edition 2004

VGB-R 450 Le
Second Edition 2004

Published by
VGB PowerTech e.V.

Obtainable from:
VGB PowerTech Service GmbH
Publisher of techno-scientific papers
P.O. Box 10 39 32, D-45039 Essen
Phone +49 0201 8128-200
Fax +49 0201 8128-329
e-mail: mark@[Link]

[Link]
Reproduction in whole or in part only
with prior permission of the publishers.
 3

Preface

EPPSA, FDBR and VGB PowerTech hereby present a European Guideline for Feed
Water, Boiler Water and Steam of Steam Generators. This new guideline replaces the
former "VGB Guidelines for Boiler Feed Water, Boiler Water and of Steam Generators with
a Permissible Operating Pressure > 68 bar, October 1988 Edition".
The present Guideline is the work of a joint European Technical Committee with
representatives of EPPSA, FDBR and VGB from most EU countries. The Technical
Committees of these organisations have discussed and agreed this guideline.
The following co-workers were involved in preparing this new Guideline:
P. Colman, ESB
K. Daucik, Elsam Engineering
M. de Wispelaere, Laborelec
D. Foussat, Alstom Power Boilers
C. Fraikin, C.M.I. Utility Boilers
B. Hausmann, FDBR
M. Herberg, Alstom Power Boiler
L. Höhenberger, TÜV Süddeutschland
B. Hughes, px limited Teesside Power Station
Dr. S. Kemppinen, Foster Wheeler Energia
T. Ruohola, Kvaerner Power
Dr. U. Staudt, VGB PowerTech
Dr. R. Svoboda, Alstom Power
U. Teutenberg, Babcock Hitachi Europe
Dr. R. Truppat, VGB PowerTech
Dr. U. Vogt, TÜV Süddeutschland
R. Wulff, Siemens Power Generation
The reader should be aware, that this guideline covers all pressure ranges applied to
boilers generating heat, steam and/or electricity. In general the guideline covers steady
state / full load operation of those boilers as well as start up operation mode by using
action levels for the first time. This concept allows a quite flexible approach to combine
requirements of the materials used throughout the steam/water cycle with economical
needs of the plant operator.
It should be pointed out that this guideline does not deliver absolute limiting values of
chemical parameters but prefers to demonstrate reasonable areas of permissible operation
ranges in respect to a minimal corrosion within the steam/water cycle to reach an
optimised lifetime of the plant. Plant specific agreements on various parameters may
supplement these guidelines.
Use it cum grano salis and as well respice finem!

Essen, December 2004

VGB PowerTech e.V.
4

Contents

Page
1 Scope.............................................................................................................. 7

2 Definitions ....................................................................................................... 8

3 Steam/water cycle system .............................................................................. 9

3.1 Feed system ................................................................................................... 9

3.2 Steam generator ........................................................................................... 10
3.3 Turbine.......................................................................................................... 11
3.3.1 Condensing Turbines.................................................................................... 11
3.3.2 Backpressure Turbines ................................................................................. 12
3.4 Condensing system ...................................................................................... 12

4 Interaction between plant design, materials and water chemistry ................ 13

4.1 Plant design .................................................................................................. 13

4.1.1 Once through boiler ...................................................................................... 13
4.1.2 Drum boiler ................................................................................................... 13
4.1.3 Combined cycle heat recovery boiler............................................................ 13
4.1.4 Waste Heat Boiler and Process Gas Cooler / Quench Boiler....................... 14
4.1.5 Boilers with gaps........................................................................................... 15
4.2 Materials ....................................................................................................... 15

5 Treatment of steam/water cycles .................................................................. 15

5.1 Purification .................................................................................................... 15

5.1.1 Make up water treatment .............................................................................. 15
5.1.2 Condensate treatment .................................................................................. 16
5.1.3 Other methods of water/steam cycle purification .......................................... 17
5.2 Deaeration and oxygen scavenging.............................................................. 19
5.2.1 Deaeration .................................................................................................... 19
5.2.2 Oxygen scavenging ...................................................................................... 19
5.3 Conditioning .................................................................................................. 20
5.3.1 Feed water conditioning................................................................................ 20
[Link] Feed water conditioning with alkalizing agents (AVT) .................................. 20
[Link] Feed water conditioning only with oxidizing agents ...................................... 21
[Link] Feed water conditioning with alkalizing and oxidizing agents (OT) .............. 21
5.3.2 Boiler water conditioning............................................................................... 21
[Link] Caustic or phosphate treatment (solid alkalizing) ......................................... 22
 5

[Link] All volatile treatment...................................................................................... 22

5.3.3 Special conditioning agents .......................................................................... 22

6 Chemical specification .................................................................................. 23

6.1 Action level control system............................................................................ 23

6.2 Operation with demineralized feed water...................................................... 27
6.2.1 Requirements on feed water for once-through boilers .................................. 27
6.2.2 Requirements on feed water for drum boilers ............................................... 29
6.2.3 Requirements on boiler water for drum boilers ............................................. 31
6.2.4 Requirements on steam for condensing turbines.......................................... 33
6.3 Operation with feed water non-demineralized............................................... 33
6.3.1 General ......................................................................................................... 33
6.3.2 Feasibility study............................................................................................. 34
[Link] Raw water / treated water parameters .......................................................... 34
[Link] Condensate percentage return ..................................................................... 34
[Link] Concentration factor...................................................................................... 34

7 Explanation of chemical specifications.......................................................... 41

7.1 pH value, acid capacity, alkalinity ................................................................. 41

7.2 Conductivity................................................................................................... 44
7.3 Oxygen.......................................................................................................... 45
7.4 Hardness....................................................................................................... 45
7.5 Phosphate ..................................................................................................... 45
7.6 Silica.............................................................................................................. 45
7.7 Iron and copper ............................................................................................. 46
7.8 Sodium / Sodium hydroxide .......................................................................... 46
7.9 Carbon dioxide .............................................................................................. 46
7.10 Organic substances ...................................................................................... 47

8 Analytical control of operation ....................................................................... 47

8.1 Sampling of Water and Steam ...................................................................... 47

8.2 Measurement ................................................................................................ 48
8.3 Monitoring ..................................................................................................... 48
8.4 Control........................................................................................................... 49
8.5 Maintenance and Calibration ........................................................................ 49
8.6 On-line measurements.................................................................................. 49
8.7 Manual controls............................................................................................. 49
6

9 Annex............................................................................................................ 50

9.1 Internal cleaning and preservation................................................................ 50

9.1.1 Internal cleaning............................................................................................ 50
9.1.2 Preservation.................................................................................................. 50
9.2 Physical-chemical processes........................................................................ 51
9.2.1 Basics of material protection......................................................................... 51
9.2.2 Deposition ..................................................................................................... 51
[Link] Deposition from water ................................................................................... 51
[Link] Deposition from steam .................................................................................. 52
9.2.3 Corrosion ...................................................................................................... 52
[Link] General ......................................................................................................... 52
[Link] Oxygen corrosion/idle corrosion ................................................................... 53
[Link] Acid corrosion ............................................................................................... 53
[Link] Caustic Corrosion ......................................................................................... 53
[Link] Hydrogen Corrosion...................................................................................... 53
[Link] Stress Corrosion Cracking ............................................................................ 53
[Link] Flow-Accelerated Corrosion.......................................................................... 53
[Link] Corrosion Fatigue ......................................................................................... 53
9.3 Economical considerations ........................................................................... 54
9.3.1 Assessment of water/steam chemistry by quality indices ............................. 54
9.3.2 Operation above Action level 3 ..................................................................... 55

10 Bibliography .................................................................................................. 57
 7

1 Scope

This guideline supports the operator of steam/water cycles in power plants and related
branches in selecting and judging suitable water regimes in respect to a safe and
economically sound operation of the power plant for a long period of time. Of course are
the showed parameter values no absolute commandment or limit - they are
recommendations and represent the bandwidth of water regimes in use. Deviations are
always possible if the plant design is specific and/or good operating experience had been
made during a long time.
Additional flexibility has been introduce by applying the “action level” philosophy. This is
true for continuous operation and especially for start up periods. The same rule applies
here: the user has to take into account the specific design of his plant and modify the
parameter limits according to the specific needs.
The guideline describes requirements to feed water, boiler water and steam of steam/water
cycles in once through and drum boilers and all pressure ranges. It is valid for salt free and
salt containing feed water. Shell boilers will be considered in the next revision.
To clarify the difference between this guideline and the EN 12952-12: the EN 12952-12
describes minimal requirements for feed water and boiler water to operate a boiler in a
safe way, the adherence to these parameters is a must. This guideline gives
recommendations that go further: not only a safe operation is looked upon, but it aims at
an economically sound and safe mode of operation for a long period of time.
This guideline is not complete: it starts with some chapters lacking that had been planned
originally. The authors had the opinion that it is more valuable to start with an incomplete
version and to begin with a broad discussion with many colleagues in the plants. Revisions
are planned and will follow in due time.
8

2 Definitions

For the purpose of this guideline the following definitions apply:

conductivity Direct measured conductivity of water.

acid conductivity Conductivity of water measured downstream of a strongly
acidic sampling cation exchanger.
all volatile treatment (AVT) Conditioning concept where only volatile alkalizing agents
are used mainly ammonia.
oxygenated treatment (OT) Conditioning concept where alkalizing agents and oxygen
are added.
caustic treatment (CT) Under this treatment boiler water pH is maintained with
sodium hydroxide.
phosphate treatment (PT) Under this treatment boiler water pH is maintained with tri-
sodium phosphate.
demineralized feed water Water with an electrolyte content according to an acid
conductivity of < 0.2 µS/cm and a silica content (SiO2) of
< 0.02 mg/l [1, 2].
non-demineralised feed Water which contains dissolved solids/matter and which
water doesn’t meet the requirements of demineralized feed water.
make-up water Water which compensates for losses of water and steam
from the system.
feed water Mixture of returned condensate and/or make up water
supplied to the boiler inlet.
boiler water Water within a natural or assisted circulation boiler.
attemperator spray water Water for injection to control steam temperature.
drum boiler Water tube boiler in which the water to be evaporated
circulates due to the differences in density (natural
circulation) or by means of pumps (forced or assisted
circulation).
once-through boiler Water tube boiler in which the water flow is effected by the
feed pump. In such the water is evaporated completely or in
a major portion during one single stage.
 9

3 Steam/water cycle system

A process diagram of a steam/water cycle system is shown in Figure 1.

Blow down

Steam Turbine Condenser Make-up

generator
water

Solid
conditioning * Filtration *
High Condensing
pressure system
heater
Ion-
exchanger *
Volatile
conditioning

Feed Feed Low

water water pressure
pump tank heater

Feed system
* optional Make-up water

Figure 1: Example for a process diagram of a steam/water cycle system.

3.1 Feed system

The basic approach to feed-water conditioning is maintenance of sufficient water purity to
limit corrosion of feed train material and to minimise the transport of corrosion products
and corrosive contaminants to the boiler. For once through boilers the only conditioning
applied will generally be to the feed-water. In this cases the quality of the steam, is directly
determined by the quality of the feed-water.
For drum boiler circuits, although further control measures may be applied in the
evaporator, it remains good practice for modern power units to have the same target with
respect to feed-water and steam.
Corrosion rarely threatens the integrity of the feed system as such. Erosion-corrosion of
mild steel components, where water velocities and turbulence are high and oxygen levels
are low, can cause damage and will also lead to enhanced iron levels which are fed
forward to the boiler. Considerable contribution to corrosion product transport to the boiler
comes from steam side of heaters, where partial condensation cause local pH
10

perturbations. Corrosion of copper alloys can be stimulated by the combined effect of

dissolved oxygen and ammonia; this can cause copper to be transported from the feed
system into the boiler and turbine.
Traditionally the chemical systems for conditioning feed-water fall into two groups:
− The reducing (ammonia or an amine with hydrazine) all volatile treatment, (AVT),
where the protection steel is based on low solubility of iron oxides at elevated pH.
− The oxidising (oxygen with a low concentration of ammonia) treatment, (OT) with very
low anion concentrations (low acid conductivity), where the protection of steel is based
on low solubility of iron oxides at elevated oxidation-reduction potential.
Although individual national and company guidelines generally specify limited
concentration ranges, overall experience indicates that these two protection mechanisms
act simultaneously and there are no distinguished border lines between these types of
conditioning. On the contrary, there is seen to be a continuum of suitable operation
conditions in a broad range with high pH and low oxygen concentration at one end, and
low pH and high oxygen concentration at the other. Achievable purity of feed-water
determines the degree of freedom available to operators within this range (high oxygen
concentrations are incompatible with chloride and sulphate contamination).
Choice of the optimal chemical conditions within this broad range will be influenced by the
boiler type, operational conditions, design and materials of construction. The presence of
the following materials is particularly important:
− Carbon steels are particularly compatible with mildly oxidising conditions in the
absence of contamination anions (chloride, sulphate, etc.).
− Copper and copper alloys may suffer oxide transport problems in oxidising regimes in
some plants and are vulnerable to attack by high levels of ammonia.
− Other materials, such as titanium, high chromium steel and chromium nickel steel are
relatively indifferent to the conditioning regime.

3.2 Steam generator

Two general classes of water tube boilers are in use:
− Once through boilers in which water is evaporated to a high steam content. These are
intolerant of non-volatile dosing chemicals and generally operate without further dosing
of the feed-water.
− Drum boilers in which steam separation takes place in an unheated vessel. Boiling
occurs in tubes through which water from the drum is re-circulated, preventing dry out
at the boiling surfaces. Such boilers may be tolerant of addition of low levels of non-
volatile alkalis to prevent any risk of acidic corrosion.
The major objectives of boiler water treatment are to minimise deposition and corrosion of
the boiler and to ensure that steam is of the appropriate quality. From the very first start of
the operation and all the way through the lifetime the boiler steel reacts with the water and
steam to produce a protective film of iron oxides. The rate of reaction decreases with time
as the thickness of the protective oxide film increases. The rate of transport of iron oxides
through the system is at its most rapid during the initial operational period.
Boiler integrity can be harmed by a number of corrosion mechanisms or by overheating
due to excessive thickness of oxide layer. The protective properties of the oxide layer are
dependent on the chemical conditions in surrounding water as well as the chemical
 11

conditions during its build up. The optimal chemical conditions are characterised by
minimum solubility of the oxide. Generally the highest possible purity, slightly alkaline pH
and appropriate redox potential are the basic parameters for integrity of the protective
oxide layer.
Non-volatile impurities concentrate in boilers and can increase the risk of corrosion. A
number of factors influence this. The build up of porous oxides by deposition onto heat
transfer surfaces is particularly detrimental. Other important factors include details of
design, construction and operating regime.
The optimum boiler water condition is mildly alkaline. Deviation either to acidic or to highly
alkaline conditions carries a risk of damage.
− Acid forming species (particularly chlorides, but also sulphates and organic anions) if
present and able to concentrate at boiler tube surfaces can result in very rapid rates of
general corrosion. This type of corrosion is often accompanied by hydrogen damage in
mild steels, which can lead to large sudden tube failures. Acids can be generated from
neutral salts particularly under oxidising conditions, and so it is particularly important to
minimise ingress of chlorides and sulphates when using oxidising treatments and
during oxygen transients at start-up for reducing treatments.
− If strong alkalis concentrate at surfaces, corrosion at unacceptable rates can also
occur. This type of attack does not normally cause hydrogen damage, but some alloys
are vulnerable to stress corrosion cracking and grooving in very high pH environments.
The required benign boiler water, which is mildly alkaline at operating temperatures and
pressures, is achieved using either an AVT or solid alkali treatment. The choice of regime
may be limited by heat flux considerations, since this has a strong effect on concentration
of non-volatile materials at boiling surfaces. Furthermore all substances that are added to
control boiler water corrosion will inevitably impact upon steam quality.
Ideally the aim is to have a zero concentration of impurities, but this is impractical and
realistic targets for both acceptable operation and limited out of specification operation are
needed.

3.3 Turbine

3.3.1 Condensing Turbines

Normally direct conditioning of steam is not applied, and hence the chemical quality of
steam derives from the measures applied to control feed water and boiler water. Thus, one
of the objectives of feed water and boiler water conditioning is to avoid deposition and
corrosion in the steam path, e.g. pipes, valves and turbine.
Steam purity must be high and actual quality is determined by:
− Vaporous carry over (volatility) of boiler water constituents. The volatility is a function
of pressure, temperature and secondary influences of other chemical components.
− Mechanical carry over of droplets of boiler water.
− Injection of feed water into steam for attemperation.
The interaction of steam impurities with turbine materials is basically determined by
deposition and by condensation of these impurities. Deposition can take place when the
solubility limit has decreased -with steam expansion- below the actual impurity
concentration. Condensation can take place when steam expansion forms water droplets
12

or water films, in which the impurities can partition in relation to their distribution
coefficients. Due to the rapid expansion of steam in the turbine, these processes may
however be too slow to reach equilibrium conditions.
The early condensation zone of the turbine is particularly sensitive to low volatility
contaminants. These impurities can concentrate on surfaces and in the very first droplets
of condensate to form an aggressive environment. Enrichment of impurities can also occur
when wet steams is locally dried up on turbine components.
Enrichment of acidic impurities leads to a decrease in local pH on turbine components,
which in turn enhances corrosion fatigue and stress corrosion cracking.
Sodium hydroxide and chlorides at certain concentrations present a particular stress
corrosion cracking risk to steels with non-heat treated welds or with austenitic structures.
On the other hand, sodium phosphates from boiler water treatment are not considered as
being aggressive to the steam turbine. They may however form salt deposits that can
impair essential turbine control (e.g. function of the turbine inlet valves).
Decomposition products of organic impurities (organic and carbonate anions) may be
implicated in turbine damage.
Silica is the most soluble of the common boiler water contaminants in high pressure steam
and has a high volatility. It can become supersaturated during expansion in the turbine.
This results in deposition on the blades causing loss of turbine efficiency, and in severe
cases, loss of output.
Salts deposited in steam pipe-work on-load can result in the development of concentrated
solutions off-load following introduction of moist air or condensation of residual steam. This
effect is particularly significant for re-heaters, turbines and some types of feed heaters. In
the turbine, it may cause pitting. Besides causing mechanical degradation, pits may also
initiate other forms of corrosion like stress corrosion cracking during the following turbine
operation.
The limits described for steam in the IEC Technical Specification TS 61 370 "Steam
turbines - steam purity" [3] are specifically designed to protect the steam turbine. This
specification is designed for new plants, but may be adapted for use on existing plant.

3.3.2 Backpressure Turbines

If the steam data (pressure, temperature) at the turbine exhaust are sufficiently high,
neither condensation nor salt deposition will take place in the turbine. Some of the steam
purity requirements for condensing turbines may therefore be exceeded in backpressure
turbines. However, this is only permitted if the composition of the steam is known and in
accordance with the steam data at the turbine exhaust. These values must be defined
plant-specifically.

3.4 Condensing system

Because condenser leakage is the major source of impurities in circuits, monitoring of
condensate is particularly important as an early indicator of the need for action. As station
circuits vary, consideration for each plant on an individual basis is necessary to ensure that
contaminated condensate is not fed to vulnerable components (such as attemporator
sprays, etc.).
 13

Units with once through boiler are always equipped with condensate polishing plant (CPP)
to take care of this problem. CPP should be designed, maintained and operated on a
standard which is able to cope with condenser leakages.
Drum boiler units are often without CPP and in case of condenser leakage precautions
must be taken to avoid damages.

4 Interaction between plant design, materials and water chemistry

4.1 Plant design

4.1.1 Once through boiler

Once through boilers are steam generators where the feed water evaporates completely
within the tubes and the rest of electrolytes would be deposited on the tube walls.
Therefore once through boilers need demineralised feed water which has to be only
conditioned with volatile agents (AVT/OT).

4.1.2 Drum boiler

Drum boilers are steam generators with natural or assisted circulation of the boiler water.
The standard procedure of boiler water conditioning is the application of solid alkalizing
agents. In this connection, particular reference must be made to the water for spray type
desuper-heaters for steam temperature control (attemperators). The spray water must be
of the same quality as demineralized feed water and must not contain solid alkalizing
agents, which would deposit in the super-heater or turbine. Operation with contaminated
feed water results as well in deposition of contaminants with serious risk of corrosion as a
consequence.

4.1.3 Combined cycle heat recovery boiler

Combined cycle power plants (CCPP) use the energy of a gas turbine exhaust for steam
production in an adjacent heat recovery steam generator (HRSG) and operation of a steam
turbine. This combination of gas and steam turbine cycles allows high efficiency power
generation. Including district heating into the cycle further increases the efficiency.
The development of combined cycle power plants started with single pressure drum-type
heat recovery steam generators and reached the state of today with triple pressure drum-
type and reheat or with a combination of once-through steam generators (OTSG) and
drum steam generators. These arrangements require thoroughly considerations regarding
the chemical treatment of low (LP), intermediate (IP) and high pressure (HP) boilers,
depending on the design and the operational conditions.
Drum steam generators may be operated with all volatile (AVT), phosphate (PT) or caustic
treatment (CT). For once through steam generators the oxygenated treatment (OT) is
recommended. Otherwise all volatile treatment has to be applied.
All volatile treatment for low pressure drum steam generators is only suitable with an
adequate high pH in the boiler feed water or with higher grade materials in the evaporator
circuit, which are resistant against flow accelerated corrosion (FAC) attack. Flow
accelerated corrosion is classified as the main cause for boiler tube failures in low pressure
14

evaporators, because the operating temperature is in that range where flow accelerated
corrosion is most likely.
The required high pH in the feed water may not always be applicable, e.g. restriction of pH
in export steam for industrial processes, and an upgrade of the material not possible. In
such case a solid alkalization of the low pressure boiler water is needed.
High pressure evaporator circuits under phosphate or caustic treatment may suffer from
under deposit corrosion (acid, caustic and hydrogen corrosion).
Heat recovery steam generators with supplementary duct firing may not be suitable for
phosphate or caustic treatment. The operation of the duct firing not-seldom results in at
least temporary local dry out of evaporator tubes, concentration of the solid alkalizing
agent and subsequent corrosion attack.
Besides efficiency flexible operation with daily or weekly shutdowns and short start-up
times as well as additional operating cost reduction (man power reduction) are actual
requirements for most combined cycle power plants.
Frequent start/stop and operation under phosphate or caustic treatment needs well skilled
chemical operators. If this cannot be assured, the chemical treatment should be as simple
as possible. The best approach in this regard is an operation with all volatile treatment.
Combined cycle power plants are also in use for cogeneration purposes, at which steam is
exported for industrial processes. A wide range of make-up water demand and return
condensate flow is possible. Special attention should be directed to the quality of the return
condensate, which might be contaminated by the process. Monitoring of the total organic
carbon (TOC) is recommended, if there is a potential for pollution with organic chemicals or
oil.
100% make-up demand or return condensate flow or a mixture of both is possible at
combined cycle power plants with back pressure turbines and at pure cogeneration plants
without steam turbine.

4.1.4 Waste Heat Boiler and Process Gas Cooler / Quench Boiler
Many waste heat boiler with operation pressure < 30 bars and common heat flux are shell
type boiler with hot gas or process medium within the tubes and boiler water around the
tubes.
Most process gas coolers e.g. of ammonia, methanol and ethylene plants (quench boiler)
are shell type boiler but show both high heat transfer (local max. heat flux up to
700 kW/m²) and operational pressure (up to 130 bars). They require particular boiler feed
water and boiler water quality.
Shell type process gas coolers and tube in tube quench boilers should have gapless welds
of the tube to tube sheet or header connection at least at the gas inlet (hot end), but same
welds are recommended for the cold end. In case of gaps or weld voids, e.g. dissolved
solids of “boiling out” solution or boiler water may be concentrated within the heated gaps
and may cause corrosion.
Demineralised boiler feed water is a presupposition for trouble free operation of these
boilers and all volatile treatment (AVT) is very advantageous. Otherwise tri-sodium
phosphate dosing according the highest pressure range of the boiler water
recommendations is necessary.
Completely flooded Salt Bath Cooler do not have excessive heat transfer and may be
operated with feed water and boiler water depending of operation pressure like normal
 15

steam generators. In case of a heated water/steam boundary (not completely flooded

cooler) the feed water and the boiler water should meet the limits for all volatile treatment
(AVT).

4.1.5 Boilers with gaps

Heated gaps allow excessive concentration of non volatile boiler water constituents and
may initiate corrosion, particularly caustic stress corrosion cracking. Boiler of such design
operated with demineralised feed water must not use sodium hydroxide for basic pH
adjustment, but appropriate phosphate treatment is recommended. AVT regime causes no
problems in such boilers but needs demineralised feed water.

4.2 Materials
Typical materials used in the steam/water cycle are carbon steel and stainless steel. For
condensate respectively feed systems often copper or copper alloys are applied because
of their good thermal conductivity.
Copper is very sensitive to complex forming agents like ammonia and is subject to
increasing corrosion rates and stress corrosion cracking in presence of ammonia or
ammonium ions, particularly in presence of oxygen. Therefore the pH value has to be
considered carefully in the presence of copper or copper alloys in the water/steam cycle.

5 Treatment of steam/water cycles

5.1 Purification

5.1.1 Make up water treatment

The necessary type of make up water treatment for boilers depends on:
− Raw water quality (e.g. hardness, alkalinity, conductivity, silica content, turbidity).
− Amount and quality of condensate return to the boiler feed water.
− Requirements on the boiler feed water and boiler water (depending on boiler type,
boiler pressure, max. heat transfer).
− Requirements on the steam produced (e.g. super-heater/turbine operation, high quality
steam for production processes, corrosion in the steam and condensate system).
− Economic and ecologic requirements (e.g. blow down rate, effluent requirements).
Make up water treatment is a demineralization process most commonly done in ion
exchanger units of different design or in case of surface water with reverse osmosis
combined with a polishing filter like e.g. mixed bed filter, electro deionisation (EDI) etc.
Before the demineralization it is often necessary to improve the raw water quality by
different pre-treatment steps (especially for high contents of organic, iron or manganese)
including chlorination, sedimentation, flocculation, filtration, oxidation, de-chlorination.

Softening
Softening is the minimum for make up water treatment, it exchanges the most important
scale forming constituents of the raw water like calcium (Ca) and magnesium (Mg)
16

compounds for sodium (Na). Its application is mostly restricted to low pressure boilers
(≤ 40 bars) with natural or forced circulation and low heat transfer rates, if there are no
further requirements to boiler operation and steam quality. Optimised condensate return is
advantageous in order to minimise the quantities of softened make-up.

Decarbonisation
Decarbonisation, in combination with softening is recommended if the raw water shows
higher alkalinity, particularly if the total alkalinity of the boiler feed water exceeds ca.
1 mmol/l. Its application is mostly restricted to boiler pressures ≤ 60 bars with natural or
forced circulation and low heat transfer rates, if there are no further requirements to boiler
operation and steam quality. Optimised condensate return is advantageous in order to
minimise the quantities of decarbonised make-up.

Partial Demineralization
Partial demineralization by reverse osmosis (RO), electro dialysis (ED/EDR) or ion
exchange reduce the content of raw water contaminants significantly (e.g. direct
conductivity < 20 µS/cm, silica content mostly < 0.2 mg/l). Partially demineralized water is
usually further polished to demineralized water.

Demineralization
Demineralization in ion exchanger plants, consisting at least of cation, anion and/or mixed
bed filters, or one of the above mentioned partial demineralisation steps in combination
with a mixed bed filter or one of the modern membrane processes driven by electrical field
(EDI), leads to demineralised water (“Demin” water). This “Demin” water is sufficient for the
operation of all steam generators and is a presupposition for safe operation of a unit with
injection spray water for steam attemperation or once through boiler [4].

5.1.2 Condensate treatment

The necessary type of condensate treatment for boilers depends on:
− Condensate quality (e.g. conductivity, corrosion products, hardness, silica content,
hydrocarbons, pollutants due to ingresses of product).
− Amount and quality of condensate return in the boiler feed water.
− Requirements to the boiler feed water and boiler water (depending e.g. on boiler type,
boiler pressure, max. heat transfer).
− Requirements on the steam produced (e.g. super-heater/turbine operation, high quality
steam for production processes).
− Economic and ecologic requirements (e.g. blow down rate, effluent requirements).
Condensate treatment consists most commonly of mechanical filtration and/or ion
exchanger units of different design.
Additional features are indicated for process return condensate. Potential presence of e.g.
hydrocarbons (oil, grease, fat) may require pre-treatment steps like skimmers or activated
carbon filters. In case of possible ingress of high risk matter, e.g. heavy fuel oil, acids or
free caustic in high concentration, separate condensate return combined should be
considered. Controlled by on-line monitoring, this condensate can then automatically be
recycled or put to waste.
 17

Overview on methods and recommendations for condensate polishing are detailed in VGB
guideline VGB-M 412 L [5].

Filtration
Filtration is highly recommended if the condensate return is continuously or frequently
contaminated with higher (approximately > 0.03 mg/l) amounts of corrosion products e.g.
Iron Oxides or non-dissolved matter.
Common methods for filtration are:
− Gravel or charcoal filters. It has to be assured that the filter material does not pollute
the condensate with e.g. hardness, silica or organics.
− Cartridge filters.
− Pre-coat filters.
− Electromagnetic filters.

Demineralization
Demineralization is required if the condensate has to have high ionic purity. For
condensate polishing, ion exchange resins are used:
− Deep bed filters.
− Powdered resin pre-coat filters.
Resins for condensate demineralization (condensate polishing) must have higher thermal
resistance and higher mechanical strength than resins for make up water treatment:
− Above 60° C the retention of silica decreases, and the resin starts to decompose,
causing loss in capacity as well as release of decomposition products (leachables) that
decompose to ionic contaminants if entering the boiler. Even the decomposition of
cation exchange resin is modest its decomposition products give serious problems by
producing strong acids (sulphuric acid) by further decomposition in the boiler. The
decomposition of anion exchange resin is substantial above 80° C and lead to loss of
capacity and fouling of cation exchange resin by decomposition products (amines).
− Resin fines and chips of resin affect the quality of both boiler water and steam. Macro-
porous resins have better mechanical stability than gel-type resins.
Deep bed filters can be carried out as mixed-bed filters, either by themselves or with
upstream cation exchanger or mechanical filters. Other combinations, like cation-/anion-/
cation-exchange beds have also proven to be of benefit.
Powdered resin pre-coat filters can be carried out by use of pre-coat mixed-bed resin,
optionally with a topping of inert filtration material.

5.1.3 Other methods of water/steam cycle purification

Even with use of the best purification technology for make-up water and condensate
polishing, some impurities will enter the water/steam cycle. These contaminants will
accumulate at certain places, where the physical-chemical conditions cause deposition
due to solubility relations. This paragraph describes possible methods to eliminate the
concentrated contaminants from time to time.
18

Blowdown
Blowdown is a well-known and generally used method to divert low volatility contaminants
accumulated in the boiler water. Blowdown is the primary tool for control of the
contaminants in the boiler water.
At commissioning and start-up continuous blowdown is necessary to reach the specified
purity of the boiler water as soon as possible. During the operation many units change to
periodic blowdown depending on the concentration of contaminants in the boiler water.
The common parameters used for blowdown are silica and acid conductivity or
chloride/sulphate (expressed by specific conductivity).
Strictly speaking blowdown is applicable on drum boilers only. However, most of the once-
through boilers have a separation vessel, which is acting at low load operation similarly to
a drum. Diversion of the “boiler water” from the separation vessel at the right time is a
useful method to eliminate the contamination accumulated in the evaporator during high
load operation. The separation vessel is dry during high load operation. The main part of
the ionic contamination accumulated in the evaporator will enter the separation vessel with
the very first water at the transition to low load. It is recommended to divert this water out
from the cycle and start the recirculation when the water from separation vessel reaches
appropriate purity.

Heaters
Steam is often used for heating purposes both internally (feed water heaters, air heaters)
or externally (district heating, industrial heating). Drain from indirect heat exchangers of
this type is usually returned into the cycle, often without any polishing. If the steam is
superheated, deposition of contaminants appears on the dry parts, where desuperheating
occurs. When wetting the dry surfaces the deposits dissolve and contaminate the
condensate drain.
Washing of deposits in a heater can be performed during operation. The procedure starts
with diversion of drain, as it is expected to pick up the deposited contamination. The
closing of the steam supply for 5 – 10 minutes results in a cooling of the heat exchange
surfaces to the temperature of the cooling medium. At the re-opening of the steam supply
the deposits dissolve in condensate appearing on the dry surface. When the contamination
is washed out, the recycling of the drain can be re-established.
Periodical washing of the deposits is recommended, particularly up to an off-load period.
The removal of the ionic deposits improves the conservation during standstill.

Re-heaters and super-heaters

Deposition of low volatile ionic contaminants from steam occurs also in re-heaters and
super-heaters, particularly at their cold ends. These deposits can be removed by washing
with saturated steam during by-pass operation of the turbine. The contaminated
condensate from this washing must be polished before reuse. The operation is quite
complicated and expensive. It can only be recommended if serious corrosion problems
appear during off-load periods due to insufficient conservation.
 19

5.2 Deaeration and oxygen scavenging

5.2.1 Deaeration
As mentioned in other chapters, the presence of oxygen and other gases plays a major
role in steam and water chemistry cycle. Even though oxygen properties are better known
and even used in specific treatments, it remains mandatory to control its level and discard
other deleterious gases such as carbonic acid, as well.
Deaeration is therefore a key word for proper reliable chemistry management. Its action is
applicable for condensates, make-up and feed water where gas may exist up to saturated
level due to long contact with ambient air or, at lower concentrations from leakages
through the balance of plant train.
The condenser and the deaerator/feed water tank are specific items of pant where
deaeration takes place.
The presence of non reactive gas in liquids is governed by their solubility, which is a
function of the temperature and partial pressure of the gas in the vapour-phase.
Deaeration principle is therefore based on the closest contact between the liquid-phase
and vapour-phase of which, said gas concentration, is lowered down to its reachable
minimum. Deaeration key parameters are:
− The best spray available to offer the greatest surface to volume ratio and speed the
transfer of the dissolved gas from the liquid phase to the vapour-phase.
− The lowest concentration of the gas in the vapour-phase performed by air extraction
and/or steam ventilation.
Dearation equipment is working close to saturation conditions depending on the
temperature characteristics of their place in the thermodynamics cycle.

5.2.2 Oxygen scavenging

During stable operation, the outlet of condensate pumps indicates dissolved oxygen
content < 15 µg/kg and outlet of deaerator < 5 µg/kg. When a reducing medium is chosen,
it may worthwhile injecting some additional conditioning chemical to implement the oxygen
removal and ensure a reducing medium1. The most commonly used scavenger is
hydrazine whose properties match all the high pressure chemistry requirements, since it
does not decompose into troublesome by products. Safety precautions must be taken
since it is classed as a category 2 carcinogen in the European Union.
Some hydrazine substitutes have proven to be effective but add carbon dioxide to the fluid
which is detrimental to the chemistry management.
For low pressure specific steam generators2, sodium sulphites may be used, noting its
salinity contribution to boiler water and potential acidic decomposition.

1
Strong reducing medium may enhance erosion-corrosion phenomenon. Taken apart protection during outages, high
hydrazine content is not advisable, nor a way to palliate a poor deaeration. Its usual excess content in the feed water
is ranging from 5 to 10 µg/kg.
2
Electrode boilers with demineralized make-up water supply
20

5.3 Conditioning
Corrosion of plant components in contact with water and steam in a water/steam cycle can
be minimized by chemical measures. A common feature of the standard conditioning
methods described here is the requirement that a minimum pH and other conditions are
adhered to and that the addition of various chemicals promotes the formation of a highly
corrosion-resistant layer on metal surfaces.
The dissolution of iron in pure, virtually oxygen-free water involves a hydrogen reaction, i.e.
the formation of iron(ll) hydroxide and hydrogen. The oxidation of Fe(ll) to Fe(lll) and the
subsequent condensation to oxides which can form a protective layer are not possible with
water as the oxidizing agent at temperatures of < 180° C. Condensate and feed water
always contain traces of oxygen, which pro-mote these reactions at the phase boundary,
thereby facilitating layer formation, albeit slowly, if the low oxygen level is matched by
correspondingly low concentrations of iron(ll) hydroxide. This condition can be satisfied by
raising the pH above the saturation pH of Fe(OH)2 (pH = 9.25 at 25° C) in order to
suppress the solubility of the iron(ll) hydroxide and thus the iron dissolution itself
(conditioning with alkalizing agents, see section 5.3.1 and 5.3.2).
Oxidation of Fe(ll) to Fe(III), the limiting stage of the Schikorr reaction with water as the
oxidizing agent, can be brought above by addition of oxygen. This greatly reduces the
solubility of the corrosion product and makes possible the formation of an oxide protective
layer, if oxidation occurs near the metal surface. The oxide layer inhibits the metal
dissolution which is determined by the solubility of the iron(ll) hydroxide, which is in turn
dependent on pH, insofar as it reduces the area where water comes into contact with
metal. Transport of corrosion products persists to a small extent through pore diffusion. If
the ratio between Fe(ll) and the oxygen concentration shifts, when a film is present, which
is caused by initial oxidation, for example, the catalyzed oxidation of Fe(ll) produced by
hydrated Fe(lll) oxide leads to a growth in the oxide layer and reduces the corrosion
product carryover to the feed water. This is the underlying principle of conditioning with
oxidizing agents.

5.3.1 Feed water conditioning

[Link] Feed water conditioning with alkalizing agents (AVT)

Ammonia is the most common volatile alkalizing agent. In demineralized water at low
temperature pH around 9.5 is necessary to achieve the minimum solubility of iron, and thus
corrosion product take-up. Correspondingly high ammonia concentration levels are usually
not permitted with brass-tubed condensers, as copper dissolution is caused by
concentrations of ammonia resulting from the design characteristics, particularly in the air
extraction zone. The alkaline conditioning thus necessitates a compromise. Because of the
iron materials, the recommended pH in the feed water is 9 or above. If copper materials
are present in the water/steam cycle the upper limit must be set according to the design
characteristics and the materials of the condenser and is generally kept below 9.4. The
upper limit to ammonia concentrations with tubing made from steel, chromium-nickel steel
or titanium is given by limits on condensate polishing plant load if any available. Air-cooled
condensers made of aluminium only permit a pH of no more than 8.
The optimum pH level for the whole plant must be established in the condensate/feed
water train upstream of the low pressure heaters to ensure maximum corrosion protection
for these heaters. Where a condensate polishing plant is installed, ammonia must
therefore be dosed upstream of the low pressure heaters. In cycles without a condensate
 21

polishing plant the ammonia only escapes from the water/steam cycle via vent in
condenser and deaerator. The addition of ammonia in accordance with the make-up water
quantity can also happen at other points, for example in the make-up water on the suction
side of the feed water pump. The latter alternative is not feasible, if large quantities of
make-up water are fed into the condenser.
Hydrazine is also sometimes used to increase pH. It is a reagent, which affect both pH and
redox potential through its reaction with oxygen.

[Link] Feed water conditioning only with oxidizing agents

Iron take-up by the feed water is reduced by dosing with gaseous oxygen, if the purity of
feed water is high. This makes it possible to dispense with alkalizing in the condensate and
feed water zone, if ammonia-free steam is desired or, if ammonia must not be present in
the water/steam cycle for any reason. The solubility of iron is greatly reduced by oxidizing
the primary corrosion product, iron (II) hydroxide, which creates the conditions necessary
for protective oxide layer formation.
Conditioning with oxidizing agents is generally used in plants with once through boilers.
Dosing with gaseous oxygen must take place upstream of the low pressure heaters. The
oxidizing agent concentration must be adjusted so as to minimize dissolved divalent iron in
the feed water upstream of the boiler inlet.
A successful application of this conditioning is based on good control of feed water purity.
Generally it requires condensate polishing plant to ensure the purity.

[Link] Feed water conditioning with alkalizing and oxidizing agents (OT)
The concentration of iron in the feed water is reduced by adding both gaseous oxygen and
ammonia. The alkalising agent promotes the oxidation process of Fe (ll) to Fe (lll) in water
containing oxygen and also offers a certain amount of protection against the harmful effect
of anions on the protective laver in the event of salt penetrations.
Oxygenated treatment is limited, with some exceptions, to plants with once-through boilers
having condensate polishing. Ammonia and molecular oxygen must be fed separately into
the feed water upstream of the low pressure heaters in concentrations, which ensure that
the conditions stipulated in Table 6.3 are fulfilled in the feed water upstream of the boiler
inlet. The small increase in pH encourages protective film formation on steel in water
containing oxygen without the ammonia reaching concentration levels harmful to copper
materials, even in the air extraction zone of a condenser. In comparison with alkaline
conditioning, the ammonia concentration of the steam condensate with combined
conditioning is so much lower that the run length of the condensate polishing plants until
ammonia ion breakthrough is considerable extended.

5.3.2 Boiler water conditioning

In drum-type boilers operating at the pressures above 1 MPa, the temperatures in the
boiler water circulating system are such that a protective layer is produced by spontaneous
magnetite formation. The solubility of magnetite depends on the pH, with a minimum at
around pH 10 (measured at 25° C). At much lower pH values, the magnetite solubility
increases considerably, likewise in the highly alkaline range. In principle, a solution
balance is established in the circulating system, which, however, is disturbed by the
evaporation process. This results in supersaturation leading to carry-over of corrosion
22

products and the depositing of corrosion products on the heated side of the evaporator
tubes.

[Link] Caustic or phosphate treatment (solid alkalizing)

The pH of the boiler water must be maintained within a specific range in order to minimize
the solubility of the magnetite and to counteract the effect of contaminants, which reduce
the pH and can be carried over with the feed water and concentrated in the boiler. This
cannot be achieved using volatile alkalising agents, because in the boiler water circulating
system they play virtually no part in increasing the pH due to their equal distribution
between water and steam in the drum and their dissociation behaviour at high
temperatures. The recommended standard procedure for drum-type boilers operating at
less than 160 bar is the application of volatile and solid alkalising agents. The aim is for the
volatile alkalising agents to maintain a pH above 9 in the condensate/feed water area and
for the solid alkalising agents to achieve satisfactory boiler water alkalinity and pH. In order
to ensure thorough mixing, the solid alkalising agent -usually sodium hydroxide or possibly
tri-sodium phosphate -must be added to the feed water downstream of the spray water
tapping point. Alternatively, the solid alkalising agents can be dosed into downcomers or to
the boiler drum, if the dosing points are designed to ensure good distribution and avoid
local overdosing.

[Link] All volatile treatment

Volatile alkalising agents can be used by themselves in the water/steam cycle of drum-type
boilers when operating with demineralised feed water on condition that the conductivity of
the boiler water can be maintained at a very low level, i.e. the ingress of trace
contaminants can be virtually eliminated. When drum-type boilers use only feed water
conditioned with oxidizing agents in accordance with section [Link] or alkalising and
oxidizing agents in accordance with section [Link] (oxygenated treatment), the oxygen
content should be maintained at the lower limit of the recommended range. The boiler
water should then be conditioned with a solid alkalising agent.

5.3.3 Special conditioning agents

The treatment chemicals described in chapter 5.3.1 and 5.3.2 are typical for power plants
and also for industrial plants. Besides those “basic” chemicals numerous organic treatment
chemicals are offered and in use, mainly in industrial plants. The chemicals can be
classified as follows:
− Neutralising/alkalising amines.
− Film-forming amines.
− Alternative oxygen scavengers (“hydrazine substitutes”).
− Dispersants.
Nearly all of these chemicals are subject to thermal degradation under boiler operating
conditions, resulting in formation of organic acids and/or carbon dioxide. The breakdown
products increase the acid conductivity in the entire steam water cycle and possible
ingress of contaminants from other sources are masked.
Concentration of the breakdown products in the first condensate of a condensing steam
turbine may result in corrosion attack.
 23

Acidic breakdown products decrease the pH of the boiler water and require the application
of solid alkalising agents.
Plants using organic treatment chemicals should thoroughly reconsider the actual chemical
regime and investigate, if the applied chemicals are really indispensable or if a reduction in
the number of chemicals is feasible. Single substances should be preferred, rather than
proprietary chemical blends.
A redesign of systems may be a worthwhile challenge to reduce the number and dosing
concentrations of organic treatment chemicals or even enable a chemical treatment
according to chapter 5.3.1 and 5.3.2 and save operating costs.
Plants with long-term good operational experience without any damages or upsets related
to the use of organic treatment chemicals may continue with the proven chemical regime,
but take the above mentioned into account.
The design of new plants should enable a chemical treatment according to chapter 5.3.1
and 5.3.2.
The application of alternative treatment chemicals requires the agreement of the boiler and
steam turbine manufacturer.

6 Chemical specification

6.1 Action level control system

The chemical control is based on specifications of normal operating values and 3 action
levels for concentrations of chemical species. The most significant parameters are defined
as key parameters and stringent control of them is required, if possible continuous
monitoring.
Other chemical measurements will frequently provide valuable diagnostic data. Laboratory
support is required for periodical extended analysis and check of monitors.
The action levels are defined which allow the operator to use the same set of limits for
continuous operation and for start-up. The detailed definitions of action levels are specified
separately for these situations in table 6.1. Action levels are time related and the
combination of concentration and time are set to minimise damage to feed, boiler and
turbine components from corrosion and deposition processes.
The limits for action levels are defined as a function of pressure. This is a simplified
approach; there are other parameters which affect the "true" limits (e.g. heat flux).
Nevertheless, pressure has been chosen as the most convenient parameter for operators.
Boilers with extraordinary high heat flux (some designs of oil fired boilers) may require
more stringent limits particularly in regard of boiler water quality.
It is the aim of the guidelines to avoid the shut-down requirement as long as there is any
realistic chance to eliminate the source of trouble. This should be managed by such
actions as load reduction to reduce heat flux (i.e. reducing the risk of damage whilst
remedial actions are being undertaken) before action level 3 limits are exceeded. Load
reductions may also be essential when feed-water contamination is encountered in order
to allow the flow of this water to attemporator sprays to be terminated without risk of
overheating.
24

When a drum boiler on AVT dosing is exposed to high levels of impurities, it can be
temporarily conditioned with solid alkali (giving it higher tolerance of impurities) and thus
delaying or avoiding action level 3.
 Responsibility
Action level or range Characterisation Action during operation Action during start-up
for action Table 6.1:

The maintenance of chemical control

N Normal operation value Operator through the monitoring of key parame-
ters should be continued.

Monitoring of the circuit chemistry

should be extended to diagnostic com-
Chemical ponents to identify the possibilities for
N - AL 1 Acceptable range
management optimisation. Strategic considerations
should be made to justify the cost of
improvement.

AL 1

Action should be taken to find and elimi- Action level 1 for key parameters
Loss of chemical control
nate the cause within one week. Further should be achieved in 2 to 8 hours
AL 1 – AL 2 possibly leading to long Operator
actions to minimise possible damage to for warm and cold starts
term damage.
the plant shall be taken. respectively.
Definitions and characteristic of Action Levels

AL 2

Fire the boiler. Check the steam

Action should be taken to find and elimi-
Loss of chemical control quality. At least action level 3 for
nate the cause within one day. Further
AL 2 – AL 3 possibly leading to short Operator all parameters should be reached
actions to minimise possible damage to
and long term damage. before turbine is brought into ser-
the plant shall be taken.
vice.

AL 3

The unit should be shut down within 1

Chemistry out of control hour using the normal shut down proce- Purge the boiler until all the key
outside AL 3 connected with imme- Shift manager dure if one of the key parameters is out- parameters are below action level
diate damage. side AL 3. For diagnostic parameters 3.
see AL 2 – AL 3.

1. The time limits may be adapted according to local requirements.

2. By exceeding the time limits the next higher AL applies, if the pending parameter is defined at this higher level.
25
26
Table 6.2: Key parameters for control of water/steam cycle

Circuit Sampling point Conditioning Key parameter

Acid Conductivity + (Direct
Drum Boiler Boiler Water AVT
Conductivity or pH1)
Acid Conductivity + (Direct
Drum Boiler Boiler Water NaOH
Conductivity or pH1)
Direct Conductivity + pH (+ Acid
Drum Boiler Boiler Water Phosphate
Conductivity, plant specific)
Acid Conductivity + (pH1 or
Drum Boiler Feed-water All
Direct Conductivity) + O22
Once through
Feed-water All Acid Conductivity + pH1 + (O23)
Boiler
Acid Conductivity + Na (in some
All Steam All
cases)

1
Instead of pH measuring the pH can be calculated from the difference of direct and acid conductivity.
2
continuous oxygen monitoring may be substituted by periodic analysis, if the deaerator performance is known to limit
possible oxygen ingress to meet feed water purity requirements
3
oxygenated treatment: continuous monitoring; AVT: continuous monitoring or periodic analysis
 27

6.2 Operation with demineralized feed water

6.2.1 Requirements on feed water for once-through boilers

Table 6.3: Once Through boilers with a copper free condensate / feed water system
FEED WATER and Attemperator Spray Water
Boiler Type Once Through; copper free condensate / feed water system
Feed Water Treatment AVT (Alkaline) OT
pH N 9.2 – 9.5 8.4 – 9.0
AL 1 9.2 9.8 8.4 9,8
AL 2 8.8 10.0 8.2 10.0
AL 3 8.2 10.2 8.0 10.4
Acid Conductivity µS/cm N < 0.10 < 0.10
AL 1 0.20 0.15
(1)
AL 2 0.30 0.20
AL 3 1 1
Conductivity µS/cm N 4.3 – 8.5 0.7 – 2.8
(only valid for ammonia AL 1 4.3 18 0.7 18
dosing) AL 2 1.7 28 0.4 28
AL 3 0.4 43 0.3 68
Oxygen (O2) µg/kg N 5 – 20 30 – 150
AL 1 2 –100 250
AL 2 > 250 500
AL 3 – –
Silica (SiO2) µg/kg N <5 <5
AL 1 20 20
AL 2 50 50
AL 3 – –
Iron (Fe), total µg/kg N <5 <5
AL 1 10 10
AL 2 20 20
AL 3 – –
Sodium (Na) µg/kg N <2 <2
AL 1 10 10
AL 2 25 25
AL 3 50 50
Organics see chapter 7.10

N: Normal Level
AL 1 (2, 3): Action Level

(1)
Once AL 2 is reached, stop Oxygen dosing
28
Table 6.4: Once Through boilers with copper in condensate / feed water system
FEED WATER and Attemperator Spray Water
Boiler Type Once Through; copper alloy in the condensate / feed water system
Feed Water Treatment AVT (Alkaline)
pH N 8.9 – 9.2
AL 1 8.8 9.3
AL 2 8.5 9.4
AL 3 8.2 9.5
Acid Conductivity µS/cm N < 0.10
AL 1 0.20
AL 2 0.30
AL 3 1
Conductivity µS/cm N 2.2 – 4.3
(only valid for ammonia AL 1 1.7 5.5
dosing) AL 2 0.9 7.0
AL 3 0.4 8.5
Oxygen (O2) µg/kg N 5
AL 1 10
AL 2 50
AL 3 100
Silica (SiO2) µg/kg N <5
AL 1 20
AL 2 50
AL 3 –
Iron (Fe), total µg/kg N <5
AL 1 10
AL 2 20
AL 3 –
Copper (Cu), total µg/kg N <1
AL 1 3
AL 2 5
AL 3 –
Sodium (Na) µg/kg N <2
AL 1 5
AL 2 20
AL 3 50
Organics see chapter 7.10

N: Normal Level
AL 1 (2, 3): Action Level
 29

6.2.2 Requirements on feed water for drum boilers

Table 6.5: Drum Boilers with a copper free condensate / feed water system
FEED WATER and Attemperator Spray Water
Boiler Type Drum; copper free condensate / feed water system
Feed Water Treatment AVT (Alkaline) OT
(1)
pH N 9.2 – 9.5 8.8 – 9,2
AL 1 9.2 9.8 8.6 9,8
AL 2 9.0 10.0 8.4 10.0
AL 3 8.6 10.4 8.2 10.4
Conductivity µS/cm N 4.3 – 8.6 1.7 – 4.3
(only valid for ammonia AL 1 4.3 18 1.1 18
dosing) AL 2 2.8 28 0.7 28
AL 3 1.1 68 0.4 68
Acid Conductivity µS/cm N < 0.10 < 0.10
(2)
AL 1 0.20 0.15
AL 2 0.50 0.20
AL 3 1 0.50
Oxygen (O2) µg/kg N 5 – 20 > 30
AL 1 2 - 100 100
AL 2 > 250 250
AL 3 - 1000
Silica (SiO2) µg/kg N <5 <5
AL 1 20 20
AL 2 50 50
AL 3 – –
Iron (Fe), total µg/kg N < 10 < 10
AL 1 20 20
AL 2 30 30
AL 3 – –
Organics see chapter 7.10

N: Normal Level
AL 1 (2, 3): Action Level

(1)
Use of oxygen scavengers see chapter 7.3
(2)
A higher value up to AL 2 may be acceptable if the increase of acid
conductivity can be attributed to carbon dioxide
30
Table 6.6: Drum Boilers with copper in condensate / feed water system
FEED WATER and Attemperator Spray Water
Boiler Type Drum; copper alloy in the condensate / feed water system
Feed Water Treatment AVT (Alkaline)
pH N 8.9 – 9.1
AL 1 8.8 9.3
AL 2 8.5 9.4
AL 3 8.2 9.5
Conductivity µS/cm N 2.2 – 3.4
(only valid for ammonia AL 1 1.7 5.5
dosing) AL 2 0.9 7.0
AL 3 0.4 8.5
Acid Conductivity µS/cm N < 0.10
AL 1 0.20
AL 2 0.30
AL 3 1
Oxygen (O2) µg/kg N 5
AL 1 10
AL 2 50
AL 3 100
Silica (SiO2) µg/kg N <5
AL 1 20
AL 2 50
AL 3 –
Iron (Fe), total µg/kg N < 10
AL 1 20
AL 2 30
AL 3 –
Copper (Cu), total µg/kg N <1
AL 1 3
AL 2 5
AL 3 –
Organics see chapter 7.10

N: Normal Level
AL 1 (2, 3): Action Level
 31

6.2.3 Requirements on boiler water for drum boilers

Table 6.7: Drum Boilers with Caustic Treatment
BOILER WATER
Boiler Type Drum
Boiler Water Treatment Caustic Treatment
Steam Pressure (MPa) <4 4 – 10 > 10
pH N 9.8 – 10.2 9.5 – 10.0 9.4 – 9.6
AL 1 9.5 10.5 9.4 10.2 9.3 9.7
AL 2 9.0 10.7 9.0 10.3 9.0 9.9
AL 3 8.5 11.0 8.5 10.5 8.5 10.2
Conductivity µS/cm N 15 – 40 8 – 25 6 – 10
AL 1 8 80 6 40 5 12
AL 2 2.5 125 2.5 50 2.5 20
AL 3 0.8 250 0.8 80 0.8 40
Acid Conductivity µS/cm N < 50 < 50 < 30
AL 1 50 50 30
AL 2 100 100 50
AL 3 250 250 100
Silica (SiO2) mg/kg N 0.25 x AL 1
AL 1 according to figure 4 respectively 5
AL 2 2 x AL 1
AL 3 –
Organics see chapter 7.10

N: Normal Level
AL 1 (2, 3): Action Level
32
Table 6.8: Drum Boilers with Phosphate Treatment
BOILER WATER
Boiler Type Drum
Boiler Water Treatment Phosphate Treatment
Steam Pressure (MPa) <4 4 – 10 > 10
pH N 9.8 – 10.2 9.5 – 10.0 9.4 – 9.6
AL 1 9.5 10.5 9.4 10.2 9.3 9.7
AL 2 9.0 10.7 9.0 10.3 9.0 9.9
AL 3 8.5 11.0 8.5 10.5 8.5 10.2
Conductivity µS/cm N 25 – 100 15 – 50 10 – 30
AL 1 > 100 > 50 > 30
AL 2 250 100 50
AL 3 500 200 100
Phosphate (PO4) mg/kg N < 15 <6 <3
Silica (SiO2) mg/kg N 0.25 x AL 1
AL 1 according to figure 4 respectively 5
AL 2 2 x AL 1
AL 3 –
Organics see chapter 7.10

N: Normal Level
AL 1 (2, 3): Action Level

Table 6.9: Drum Boilers with AVT (Alkaline) Treatment

BOILER WATER
Boiler Type Drum
Boiler Water Treatment AVT (Alkaline)
Steam Pressure (MPa) <8 8 – 16 > 16
(1)
pH N pH is controlled by pH of the feed water
Acid Conductivity µS/cm N <5 <3 <1
AL 1 5 3 1
AL 2 10 6 2.5
AL 3 20 12 5
Silica (SiO2) mg/kg N 0.25 x AL 1
AL 1 according to figure 4 respectively 5
AL 2 2 x AL 1
AL 3 –
Organics see chapter 7.10

N: Normal Level
AL 1 (2, 3): Action Level

(1)
pH feed water > 9.5
 33

6.2.4 Requirements on steam for condensing turbines

Table 6.10: Steam
STEAM for steam turbines

(1)
Acid Conductivity µS/cm N 0.10
AL 1 0.20
AL 2 0.50
AL 3 1
Silica (SiO2) µg/kg N <5
AL 1 20
AL 2 –
AL 3 –
Boiler Water Boiler Water
Treatment AVT or Caustic Treatment Phosphate
Sodium (Na) µg/kg N <2 <5
AL 1 5 10
AL 2 10 20
AL 3 20 40
Iron (Fe), total µg/kg N <5
AL 1 20
AL 2 –
AL 3 –
Copper (Cu), total µg/kg N <1
AL 1 3
AL 2 –
AL 3 –

N: Normal Level
AL 1 (2, 3): Action Level

(1)
Higher action values may be defined if the increase of acid conductivity can
be attributed to carbon dioxide from air inleakage and organic decomposition
products can be excluded.

6.3 Operation with feed water non-demineralized

6.3.1 General
For economical reasons, non-demineralised water may be used in some specific cases1.
Non-demineralised water is a water which still contains dissolved solids such as
decarbonisated water or/and softened water.
This water is used when the make-up rate to water cycle is low. This may be the case for
process steam supply to industry or town power cycle. Then, the feed water is composed
of condensates return mainly, mixed with a slight proportion of "non-demineralised" make-
up.

1
Industry, low pressure unit
34

The feasibility of this kind of make-up is directly linked to the raw water characteristics,
water treatment, ratio of make-up/condensates and main design/characteristics1 of the
steam generator. Each case must be specifically studied to estimate its feasibility and
compliance with these recommendations.

6.3.2 Feasibility study

[Link] Raw water / treated water parameters

Considering non-demineralised water make-up, several parameters have to be checked
since the water treatment removes them partly or not. These parameters are mainly silica,
chlorides and salinity. Total alkalinity is a key parameter for softened water, namely.2 In
any case, hardness must be fully eliminated.

[Link] Condensate percentage return

To assess the feed water quality, it is necessary to know both amount and quality of the
Condensate return2. In closed cycle (either from process or with a condenser) this quality
will improve in time, due to the purification achieved in the boiler, through the blow-down.

[Link] Concentration factor

The mineral species are concentrated in the boiler water. Alkalinity is decomposed in the
boiler to give caustic. Since a maximum concentration is given in the boiler water3, blow-
down is necessary to keep the water within the limits. This is particularly true for
conductivity, silica, alkalinity and strong acid salts.
The boiler blow-down rate is the decision parameter to judge on the feasibility. In some
case, blow-down recovery can be considered after thermodynamic balance calculus.
However, in other cases, due to the low condensates return - or poor quality - or high
salinity of raw water, this kind of water is not suitable and demineralized water only is the
issue.

1
None of these water qualities are suitable for attemperator spray water!
2
Total organic carbon must always been checked
3
Steam quality (silica, hardness) and water conditioning are to be assessed
 35
Table 6.11: Feed water for drum boilers
FEED WATER
Boiler Type Drum
Steam Pressure (MPa) <2 2-4 >4
(1) (1,2) (1) (1)
pH N 9.2 – 9.5 9.2 – 9.5 9.2 – 9.5
(1,2) (1,2) (1)
AL 1 9.2 9.5 9.2 9.5 9.2 9.5
(1,2) (1,2) (1)
AL 2 8.8 10.0 8.8 10.0 8.8 10.0
(2) (2)
AL 3 8.0 10.5 8.0 10.5 8.0 10.5
Conductivity µS/cm not specified – consider boiler water
Total Hardness (Ca + Mg) mmol/kg N < 0.005 < 0.005 < 0.005
AL 1 0.02 0.01 0.005
AL 2 0.05 0.02 0.01
AL 3 0.2 0.2 0.1
Silica (SiO2) µg/kg not specified – consider boiler water
Iron (Fe), total µg/kg N < 30 < 20 < 10
AL 1 50 30 20
AL 2 200 100 50
AL 3 – – –
Copper (Cu), total µg/kg N <3 <3 <3
AL 1 20 10 3
AL 2 50 25 10
AL 3 – – –
Oxygen (O2) µg/kg N 5 5 5
AL 1 20 20 20
AL 2 50 50 50
AL 3 100 100 100
Oil / Grease / Organics see chapter 7.10

N: Normal Level
AL 1 (2, 3): Action Level

(1)
with copper alloys in the system the pH value shall be maintained in the
range 8.7 to 9.2
(2)
with softened make-up water (pH > 7) the pH value of boiler water according
to table 6.12 - 6.14 should be considered
36
Table 6.12: Boiler water for drum boilers with saturated steam design
BOILER WATER
Boiler Type Drum, saturated steam design
Feed Water conductivity > 30 µS/cm (high-salinity content)
Boiler Water Treatment Alkaline
Steam Pressure (MPa) <2 2-4 >4
pH N 10.8 – 11.5 10.8 – 11.5 10.5 – 11.0
AL 1 10.5 12.0 10.5 11.8 10.3 11.5
AL 2 10.0 12.2 10.0 12 10.0 11.8
AL 3 9.5 12.5 9.5 12.3 9.0 12.0
Conductivity µS/cm N < AL 1
AL 1 pressure dependent according to figure 2
AL 2 1.2 x AL 1
AL 3 1.5 x AL 1
Alkalinity (AP) mmol/kg N 2–5 2–5 1–2
AL 1 1 15 1 10 0.5 5
AL 2 – – – – – –
AL 3 – – – – – –
Silica (SiO2) mg/kg N < AL 1
AL 1 pressure and alkalinity dependent according to figure 4
AL 2 1.25 x AL 1
AL 3 –
(1)
Phosphate (PO4) mg/kg N 15 10 10
AL 1 10 20 8 15 8 15
AL 2 30 25 20
AL 3 50 50 50
Organics see chapter 7.10

N: Normal Level
AL 1 (2, 3): Action Level

(1)
if used
 37
Table 6.13: Boiler water for drum boilers with superheated steam design
BOILER WATER
Boiler Type Drum, superheated steam design
Feed Water conductivity > 30 µS/cm (high-salinity content)
Boiler Water Treatment Alkaline
Steam Pressure (MPa) <2 2-4 >4
pH N 10.8 – 11.5 10.8 – 11.5 10.5 – 11.0
AL 1 10.5 11.8 10.5 11.7 10.3 11.3
AL 2 10.0 12.0 10.0 11.8 9.5 11.5
AL 3 9.0 12.5 9.0 12.5 9.0 12.0
Conductivity µS/cm N < AL 1
AL 1 pressure dependent according to figure 2
AL 2 1.2 x AL 1
AL 3 1.5 x AL 1
Alkalinity (AP) mmol/kg N 2–5 2–4 1–2
AL 1 1 8 1 5 0.5 2.5
AL 2 – – – – – –
AL 3 – – – – – –
Silica (SiO2) mg/kg N < AL 1
AL 1 pressure and alkalinity dependent according to figure 4
AL 2 1.25 x AL 1
AL 3 –
(1)
Phosphate (PO4) mg/kg N 15 10 8
AL 1 10 20 8 15 8 12
AL 2 30 25 20
AL 3 50 50 50
Organics see chapter 7.10

N: Normal Level
AL 1 (2, 3): Action Level

(1)
if used
38
Table 6.14: Boiler water for drum boilers
BOILER WATER
Boiler Type Drum, superheated steam design
Feed Water conductivity 30 µS/cm (low-salinity content)
Boiler Water Treatment Alkaline
Steam Pressure (MPa) 6 >6
pH N 10.2 – 10.6 10.0 – 10.2
AL 1 10.0 11.0 9.8 10.5
AL 2 9.5 11.5 9.4 11.0
AL 3 9.0 12.0 9.0 11.5
Conductivity µS/cm N < AL 1
AL 1 pressure dependent according to figure 3
AL 2 1.2 x AL 1
AL 3 1.5 x AL 1
Alkalinity (AP) mmol/kg N 0.3 – 0.8 0.2
AL 1 0.1 1.0 0.1 0.3
AL 2 – – – –
AL 3 – – – –
Silica (SiO2) mg/kg N < AL 1
AL 1 pressure and alkalinity dependent according to figure 4 or 5
AL 2 1.25 x AL 1
AL 3 –
(1)
Phosphate (PO4) mg/kg N 8 6
AL 1 5 10 <6 >6
AL 2 20 10
AL 3 50 30
Organics see chapter 7.10

N: Normal Level
AL 1 (2, 3): Action Level

(1)
if used
 39

7000
saturated steam
6000
superheated steam
conductivity (µS/cm) I

5000

4000

3000

2000

1000

0
0 1 2 3 4 5 6 7
pressure (MPa)

Figure 2: Drum boiler water (feed water with high-salinity), conductivity versus pressure.

1600

1400
conductivity (µS/cm) I

1200

1000

800

600

400

200

0
0 1 2 3 4 5 6 7 8 9 10 11
pressure (MPa)

Figure 3: Drum boiler water (feed water with low-salinity), conductivity versus pressure.
40

180
I

160 alkalinity 15 mmol/kg

alkalinity 10 mmol/kg
maximum silica content (mg/kg)

140
alkalinity 5 mmol/kg
120 alkalinity 0.5 mmol/kg
100

80
60

40

20

0
0 1 2 3 4 5 6 7
pressure (MPa)

Figure 4: Drum boiler water (feed water non-demineralized), silica content versus pressure to achieve less
than 0.020 mg/kg in the steam.

10
based on 0.020 mg/kg silica in steam
.

based on 0.005 mg/kg silica in steam

maximun silica content (mg/kg)

0,1

0,01
6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
pressure (MPa)

Figure 5: Drum boiler water (feed water demineralized), silica content versus pressure to achieve less than
0.020 mg/kg or 0.005 mg/kg respectively in the steam.
 41

7 Explanation of chemical specifications

7.1 pH value, acid capacity, alkalinity

pH value
The unit-less pH value is a very important unit of measurement for the acidic (pH < 7),
neutral (pH = 7) or alkaline (pH > 7) reaction of liquids, particularly water samples of water-
steam-circuits. Because of the definition of the pH-value (negative decadic logarithm of the
concentration of hydrogen ions) any step of a pH-unit is an actual change of the acidic or
alkaline concentration for a factor of ten!
For exact results the pH value must be measured electrochemically using pH-meter and
electrodes, indicators give rough information only. The pH value changes significantly with
the temperature and must be either noted together with the measuring temperature or
corrected to a reference temperature of 25° C, see Figure 6.
Corrosion of unalloyed and low-alloyed steels commonly used in boiler plants is affected
considerably by the pH. The required pH can be established in boiler water by dosing
(conditioning) with non-volatile alkalising agents (e.g. caustic soda and tri-sodium
phosphate, see Figure 7) and in feed water and condensate by conditioning with volatile
alkalising agents (e.g. ammonia, amines, hydrazine, see Figure 8). As far as possible,
their combined use, with continuous dosing, should be aimed for.
The pH must be limited in the feed water, boiler water and condensate to prevent attack on
certain metals, dissolution of iron protective layers and to avoid foaming of the boiler water.
Due to the increasing solubility of the protective layers of iron oxide in acidic solutions
aqueous samples of water-steam-circuits should be basically alkaline, see Figure 9.

Acid capacity
Acid capacity is a titration method to measure and to calculate the amount of both
− strong alkaline substances (acid capacity to pH 8.2) like caustic alkalis and
− free caustics of alkali-carbonates, tri-alkali phosphates and di-alkali silicates as well as
− strong alkaline volatile substances like ammonia or amines and
− weak alkaline or neutral substances with hidden alkaline power (acid capacity to
pH 4.3) like alkali or ammonia/amine bicarbonates and di-phosphates respectively.
The unit of the acid capacity is mmol/l (measured with a single base acid like hydrochloric
acid) or meq/l. 100 mg/kg CaCO3 correspond an acid capacity of 2 mmol/l or 2 meq/l.
The correlation between pH and acid capacity can be seen in Figure 10.

Alkalinity
Alkalinity is similar to the acid capacity and divided into
− total alkalinity – comparable to acid capacity to pH 4.3 and
− caustic alkalinity - comparable to acid capacity to pH 8.2.
42

Significant difference to the latter is a particular treatment with barium chloride to obtain the
real amount of free caustic alkali – without influence of carbonates, phosphates and
silicates.

10

9
pH-value

5
0 100 200 300 400
°C

pure water 1.5 mg/kg ammonia 10 mg/kg trisodium phosphate

Figure 6: pH influence of 1.5 mg/kg ammonia (NH3) respectively 10 mg/kg tri-sodium phosphate (Na3PO4) to
pure water depending of temperature

10

9,5

9
pH-value

8,5

7,5

7
0,001 0,01 0,1 1 10
mg/kg

sodium hydroxid trisodium phosphate

Figure 7: Increase of pH value at 25° C in pure water by non volatile alkalising agents sodium hydroxide
(NaOH) and tri-sodium phosphate (Na3PO4)
 43

10

9,5

9
pH-value

8,5

7,5

7
0,001 0,01 0,1 1 10
mg/kg

ammonia hydrazine

Figure 8: Increase of pH value at 25° C in pure water by volatile alkalising agents ammonia (NH3) and
hydrazine (N2H4)

-2
-3
-4
-5
10 mol/kg Fe(III)

-6
-7
-8
x

-9
-10
-11
-12
2 3 4 5 6 7 8 9 10 11 12 13 14
pH-value (25 °C)

Figure 9: Magnetite (Fe3O4) solubility at pH 3 to 13

44

KB 8,2 KS 8,2

p colourless phenolphthalein red p

8.2
strongly acidic weakly

pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 pH

weakly basic strongly

4.3

m red methyl orange yellow m

KB 4,3 KS 4,3

Figure 10: Interrelation between pH value and acid- (KS) respectively base-capacity (KB)

7.2 Conductivity
The electrical conductivity is a measure for the sum of all dissociated substances (salts,
acids, bases and some organic substances) in liquids and is the actual substitute for the
value of total dissolved solids/matter (TDS), particularly for TDS < 1 mg/l.
The unit for conductivity is Siemens (S) per metre (m) corresponding to 1/(Ohm m) and is
expressed in 1 S/m , 104 µS/cm or 103 mS/m.
The conductivity changes strongly by the temperature and must be either noted together
with the measuring temperature or corrected to a reference temperature of 25° C. The
temperature correction factor is not constant and depends on the type of electrical
conductive matter and the absolute value of the conductivity, particularly < 0.2 µS/cm.
The conductivity of the purest water at 25° C is approximately 0.055 µS/cm.
Conductivity is the direct measured specific conductivity of any liquid.
Acid conductivity is the conductivity measured downstream of a strong acidic cation
exchanger (sampling filter) which results in the elimination of any cation (like ammonia,
sodium, potassium) and the emission of H+-cations. In that case, salts change to its free
acids e.g.
NaCl + H+-cation exchanger → HCl + Na-cation exchanger.
Bases, however, like ammonium or sodium hydroxide reacts to water e.g.
NaOH + H+-cation exchanger → H2O + Na-cation exchanger.
Acids, also carbonic acid, are passing the cation exchanger without any effect.
This is an advantage for the indication of traces of salts (e.g. of condenser leaks) in water
samples alkalised with ammonia, because acids have a significant (4 to 7 times) higher
specific conductivity than its neutral salts. On the other hand it prevents the indication of
leaks of e.g. caustic soda in water samples.
 45

Increasing conductivity in water samples promotes corrosion processes, particularly in

presence of oxygen. Elevated conductivity in BW may lead to carry over and poor steam
quality.

7.3 Oxygen
Concentration of dissolved oxygen is generally used as a parameter to express the
oxidation or reduction potential (redox potential) of an aquatic solution. This use is found to
be the most appropriate for practical purposes, even though it is biased by insufficient
equilibrium of the system. The solution can simultaneously contain oxygen, other oxidation
agents and even reduction agents, which did not react so far.
The assessments of oxygen concentration have to be made together with pH and purity of
the system (acid conductivity). High purity of the water allows increased concentrations of
oxygen and decreased pH, resulting in better protection of steel. The improvement of the
protection is caused by an oxidation of the surface of the magnetite protective layer to
hematite. Hematite has lower solubility and much finer crystalline structure and seals the
porous magnetite structure.
If high purity of the water is not achievable, the protection must relay on increased pH at
low oxygen concentrations. However, the extremely low oxygen concentration achievable
by addition of strong reducing agents (oxygen scavengers) should be carefully considered,
as the reduction of the magnetite layer result in increase of its solubility and tendency to
flow assisted corrosion.

7.4 Hardness
Hardness is a measure for the sum of all alkaline-earth elements, like calcium and
magnesium (rarely also barium and strontium) compounds in water samples and an
indicator for the risk of scale formation due to hardness (hardness scale). Deposition on
heated surfaces leads to uneconomic operation and may lead to material over-heating and
to corrosion underneath the scale due to concentration of dissolved solids.
The SI-unit for hardness is mmol/l. 1 mmol/l corresponds to 100 mg/l CaCO3.
Hardness and silica together may lead to particular scale with very low heat transfer rate.

7.5 Phosphate
Phosphate in form of alkali phosphates – mostly tri-sodium phosphate – is used for both
− alkalisation agent, see Figure 6 and
− scale inhibitor to prevent hardness scale.
Due to the particular solution behaviour of tri-sodium phosphate tri-sodium phosphate is an
alkalisation agent for boilers with heated gaps or heated phase boundaries because of its
significantly reduced solubility > 250° C.
Due to the particular solution behaviour phosphate tends to local deposit formation so
called “hide out” on surfaces with high heat transfer. In case of phosphate dosing therefore
the specified concentration in boiler water must be reduced with increasing pressure.

7.6 Silica
Silica concentrations in the feed water of once-through boilers and the boiler water of
drum-type boilers must not exceed certain values because of the requirement concerning
46

steam purity for turbine operation. The solubility of silica in steam increases with pressure.
When operating with fully demineralized make-up water, the silica concentration in the feed
water and steam of once-through and drum- type boilers remains far below the specified
values in Tables 6.3 and 6.6 and 6.10.
Even when the specified values are complied with, silica deposits in the high pressure
section of the turbine cannot be excluded under the most unfavourable conditions,
especially in the presence of substances such as aluminium.
If there are differences between the silica concentration in the feed water and in the steam
or if the silica concentration in the boiler water is higher than the product of concentration
coefficient and silica concentration of the feed water, then the raw water probably contains
colloidal silica, which was not retained in the make- up water treatment plant and has
hydrolysed to form soluble silica in the boiler.

7.7 Iron and copper

Iron and copper concentrations in feed water and steam are an indicator of the efficiency of
conditioning. They supply information on the metal dissolution processes in the system and
the metal take-up by the water as well as possible deposits in the boiler and turbine.
Changes in iron and copper concentrations due to load fluctuations cannot be influenced
by chemical measures.
In respect of corrosion product absorption, we again refer to the requirement that
condensates should not influence the characteristics of feed water or boiler water.

7.8 Sodium / Sodium hydroxide

Sodium is used to condition the boiler water of drum-type boilers in the form of sodium
hydroxide and tri-sodium phosphate, but it also occurs as a contaminant in the
water/steam cycle through slippage from ion exchangers or heat exchanger leakage.
Measuring the conductivity or the sodium level with an ion-sensitive (pNa) electrode is a
sensitive indicator of impurity ingress, typically due to cooling water.
In plants with drum-type boilers, whose water is conditioned with solid alkalizing agents,
the sodium concentration in the steam complies with the normal operating value in
Table 6.10, if the sodium hydroxide or tri-sodium phosphate concentrations are held within
the pH and phosphate limits in Tables 6.7 and 6.8. Levels which exceed the specified
values point to unfavourable water/steam separation in the drum and boiler water droplet
entrainment. Carry-over of sodium compounds to the steam can result in super-heater and
turbine deposits possibly also in corrosion.

7.9 Carbon dioxide

Carbon dioxide is a common contaminant in the steam water cycle that leads to an
increase of acid conductivity.
Depending on the quantity of air entering the steam water cycle, as well as on cycle
capabilities for degassing (condenser, deaerator) and demineralisation (condensate
polishers), some residues will remain circulating through the systems.
Another source is thermal decomposition of organic matter that has entered the cycle.
Besides carbon dioxide, other decomposition products, e.g. organic acids may be formed.
 47

If an increase in acid conductivity can be attributed to air in-leakage and organic

decomposition products can be excluded, relaxed action levels and schedules on acid
conductivity can be defined, according to operator and turbine supplier'
s experience.

7.10 Organic substances

Organic substances, which are carried over with the feed water into the steam generator,
can, after being concentrated in the boiler water of drum-type boilers, increase its foaming
tendency, cause carry-over of boiler water droplets and thus indirectly affect the steam
quality. Decomposition products of organic substances formed under boiler conditions can
directly affect the pH of boiler water and, if volatile, the steam quality [6].
Organic substances in the water are best detected by determining the dissolved organic
carbon (DOC) content. The DOC content of demineralised make-up water should not
exceed 0.2 mg/l (the knowledge of the type of organics is very important and not the sum
parameter DOC). It is recommended to strive for less than 0.1 mg/l. Even this value may
be too high in special cases, depending on the nature of the organic matter and the make-
up water demand. High make-up rates require a minimization of the DOC content.
Where organic substances can enter the steam water cycle from other sources, e.g. return
of non-purified condensate in industrial power plants, continuous monitoring of the DOC
content in the condensate or feed water is recommended. When operating with
demineralised feed water, the effects of such ingresses usually can also be detected due
to the shift of some other measured parameters, for example a decrease in the pH of the
boiler water, an increase in the acid conductivity of steam or the occurrence of a difference
in acid conductivity between feed water and steam as a result of the decomposition of
organic substances.
It is not possible to specify generally applicable specified values. Where necessary,
assessment criteria must be established concerning the influence of oil, other organic
substances or their decomposition products and concerning the maximum permissible
DOC content based on specific operating experience and requirements.

8 Analytical control of operation

8.1 Sampling of Water and Steam

It cannot be emphasised enough, that:
“Poor sampling gives poor results”
Too often “chemists” carry out extremely sensitive and complex analysis which,
undoubtedly area accurate but if the sample is flawed the results are meaningless. For
example, leaking unions on sample coolers allowing air ingress prior to deaerator
efficiency monitoring, or cooling water ingress, contaminating the cooled sample. These
samples may show high oxygen or high acid conductivity – but is this a function of
sampling or a problem with plant conditions?
Decisions and communication need to be clear as to WHAT is sampled and from where.
Typical sample points should include, but not be limited to:
− demineralized or non-demineralized water make-up feed,
− condensate returned to the make up,
48

− feed exit the deaerator,

− recirculating boiler water,
− saturated steam.
The physical conditions of the process fluid e.g. temperature, pressure, rate of flow and the
limitations of the analytical technique need to be considered and suitably designed
sampling facilities installed. There are standards for the sampling of key fluids e.g.
superheated and saturated steam where iso-kinetic sampling is recommended as
mandatory for meaningful results. It is vital to take a safe representative sample.
Sample conditioning is equally as imperative e.g. temperature, pressure and flow of the
final sample should be normalised and kept constant for the most accurate and
reproducible results. Settlement of solids in the sample-line needs to be avoided whilst
erosion-corrosion of the sample line must not occur. The choice of materials for the sample
line and cooler needs to be selected with care for the various duties.
The length of run of a sample line should be kept as short as is practical to avoid
complications from delays in changes in plant conditions to the arrival of samples at the
analyser although short lag times can be accommodated in the process control loops.
Sample line residence time and materials choice become even more critical where “grab”
samples are taken. Ideally all samples should be run continuously, at constant rate. Any
change in rate (e.g. an operator opening the sample valve to get a quicker flow to fill a
bottle more rapidly) may pick up material that has settled behind needle valves or in
horizontal runs of pipe, leading to analytically correct, but process-wise, misleading values.
The choice of the container for discrete samples is critical e.g. do not use glass bottles for
sodium analyses or plastic containers for carbon dioxide. Sample-lines that are isolated
need to be run until freshly removed fluid has completely filled the line and stable
conditions have been established.
There are arguments for On-line Analysis and for discrete samples, analysed and
monitored on a much reduced frequency which, provided the above considerations are
catered for, devolve to one of economics regarding cost of acquiring the data versus the
hysteresis of the system for reliable control. Such decisions should be made on a case by
case basis, subject to analysis of process capability. A closed loop control system can be
used to regulated the process for the desired determinant set point in the operation e.g. pH
in boiler water.

8.2 Measurement
The choice of determinants needs to be made on a case by case basis, depending on the
chosen chemistry of the station. Details of chemistries, levels, ranges and, by definition,
the required parameters to monitor and control them, are given in Chapter 6. From this,
analytical requirements can be selected.
However, accuracy, reproducibility, calibration and reliability should be taken into account.

8.3 Monitoring
Parameters change on Power Plants and inter-relate with each other, often in predictable
ways but occasionally with unexpected side effects. It is strongly recommended that an
inter-active data base is operated with a facility to plot a minimum of any four parameters
simultaneously over any time period to enable lateral thinking of chemical and temporal
effects. This is often the case for plant based systems, through DCS technology, but it is
 49

strongly recommended that the same functionality and sophistication is applied to

laboratory based measurements.

8.4 Control
Process control is best maintained by selecting a single, primary determinant; analysing for
that determinant in a sample of the process fluid that needs to be controlled and altering
the process accordingly. For example, in a phosphate/oxygen scavenger/alkalizing agent
dosed boiler all three chemicals can have an impact on pH and conductivity but it is
recommended that control is affected by three separate steps:
1. In the feed - measuring direct and acid conductivity for calculating pH and
dosing alkalizing agent continuously and automatically to a set
point which is in the middle of the “N” range.
2. In the feed - measuring oxygen and dosing scavenger continuously to a set
point which is in the middle of the “N” range.
3. In the boiler - measuring pH and dosing phosphate to a set point which is in the
middle of the “N” range.

8.5 Maintenance and Calibration

Requirement for dedicated articifers on the plant is necessary to maintain and calibrate
instruments on a daily basis if necessary. The laboratory results should plot deviations
from norm over a long time periods and report accordingly.

8.6 On-line measurements

(This chapter will be considered in the next revision.)

8.7 Manual controls

(This chapter will be considered in the next revision.)
50

9 Annex

9.1 Internal cleaning and preservation

9.1.1 Internal cleaning

The topic of internal cleaning plays an important role in reaching the aim of this guideline,
enabling boiler operation that is as trouble-free as possible as well as good steam quality
for the operation of turbines. If the Water-Steam-System isn’t cleaned properly and
professionally problems for the operation of the plant will recur leading to poor availability
and possible damage to the system.
In the power plant industry there are numerous company-specific or proprietary guidelines
and specifications for internal cleaning and steam blowing. Independent guidance can be
found in VGB guideline, VGB R 513 “Internal Cleaning of Water-Tube Steam Generating
Plants and Associated Pipe-work” [7] which is generally agreed upon by the power plant
industry. This guideline is intended to give recommendations for:
− Flushing,
− alkaline boil-out,
− preoperational acid cleaning of new plants,
− chemical cleaning of plants under operation,
− steam blowing of water-tube generating plants and associated pipe-work upstream to
the turbine, where required.
When selecting the type and performance of the cleaning procedures, agreement shall be
reached between the (steam boiler/pipe-work/turbine) manufacturers and the plant user
and be stipulated in writing. This agreement should be reached as early as possible in the
design stage.

9.1.2 Preservation
Preservation means any method to avoid corrosion on the waterside of boilers, parts of it
or auxiliary components made of low-alloyed steel during shut down and stand-by. It also
includes storage and transportation, erection and commissioning of plant. This can be
realized by excluding either oxygen or water respectively.
A sufficient present protective layer of iron oxides on the waterside of boilers (in operation
for at least 1 month before shut down) can protect low-alloyed steel in presence of
humidity or moisture and air for restricted time only. If non-demineralised BFW/BW is used
the time without preservation is restricted to 1 week, in case of the use of demineralised
BFW/BW the shut down time without preservation should not exceed 2 weeks. Exceeding
times require preservation methods by either
− wet preservation (in absence of air) e.g. by replacing of air by nitrogen or
complete kept filling of the boiler with alkaline water containing oxygen scavenger, or
− dry preservation (in absence of moisture) by drying with desiccants, e.g. silica gel or
regenerative circulating dryers.
 51

Details may be obtained from special papers (for example VGB R116 H “Preservation of
Power Plant Systems”) [8].
High-alloyed or stainless steel may require particular preservation methods to avoid
chloride induced pitting or SCC in special cases during transport, storage and stand by.
Preservation on the flue gas side of boilers may be necessary too, particularly on coal and
oil fired boilers.

9.2 Physical-chemical processes

9.2.1 Basics of material protection

The corrosive attack of water or steam on steel leading to the formation of iron oxides is
naturally limited if a protective layer, i.e. a dense and uniform oxide layer forms on the
surface of the steel. The only iron oxide, which can exist in direct contact with the metal, is
magnetite, on which oxides of trivalent iron can grow, depending on the redox conditions.
Such protective layers restrict the transport of corrosion products to pore diffusion and
reduce the area available for reaction between steel and water or steam, thereby
minimizing the material loss rate (surface layer passivity).
The basic chemical reaction between iron (steel) and water involves iron dissolution
through several reaction stages - a redox stage Fe(ll) - Fe(lll) and condensation stages
(Schikorr reaction) - to the thermodynamically stable end product, magnetite. The kinetics
of the Schikorr reaction show marked temperature dependency which is characterized by
inhibition of the redox stage. Oxidation of the divalent iron by water needs particular
configurations and conditions, which only occur in exceptional cases at low temperatures
(5.3). On the other hand, magnetite is spontaneously formed at temperatures, when
condensation of iron(ll) hydroxide is possible. The steel is covered by a protective layer.
3 Fe + 4 H2O Fe3O4 + 4 H2 (9.1)
Based on these interactions, water/steam cycles in power plants can be divided into two
areas:
− the temperature range up to around 200° C, where an inhibited Schikorr reaction
assures that the steel surface in contact with water remains active in respect of iron
dissolution and
− the hot water area from around 200° C, where the magnetite protective layer forms
spontaneously.
Iron dissolution is at maximum at around 150° C.
In the condensate/feed water line, i.e. near the LP pre-heaters at low and medium water
temperatures, the iron dissolution in pure water is normally diffusion controlled. It can
change into erosion-corrosion under unfavourable local flow conditions. Conditioning is
needed to reduce corrosion and corrosion product pick-up by the feed water.

9.2.2 Deposition

[Link] Deposition from water

Iron(ll) hydroxide as the dissolved corrosion product of iron, whose solubility decreases as
the temperature increases, tends to form supersaturated solutions above 200° C. At points
of high turbulence, e.g. around boiler control devices, or on heating faces subjected to high
52

heat fluxes, magnetite precipitates out from such solutions in crystalline form. This leads to
reductions in cross-section or hampers the heat transfer in steam generation tubes and
can cause damage to materials due to overheating.
Undissolved, suspended corrosion products, which are carried with the feed water into the
boiler or are produced in the boiler itself, can form deposits, especially on thermally
stressed tube walls and these normally have a detrimental effect. On the one hand, such
deposits can affect the heat transfer which causes the tube wall temperature to rise,
leading to overheating and rupture of the tubes due to hydrogen damage from enhanced
reaction between iron and water. On the other hand, electrolytes dissolved in the water can
concentrate under deposits, thereby initiating a chemical attack on the tube material or
protective layer. The concentration of electrolytes depends on the heat flux (evaporation
intensity) and the electrolyte concentration in the bulk water.

[Link] Deposition from steam

Impurities in steam can deposit on super-heaters, control devices and turbine blades and
lead to corrosion and a decrease of the turbine efficiency.
Dissolved solids enter the steam by physical or chemical carry-over. The physical carry-
over of boiler water droplets is typical for drum boilers only. Satisfactory water/steam
separation in drum should be ensured by appropriate design measures. However,
operational conditions have significant effect on mechanical carry-over. Disturbance of the
control of boiler water level in the drum is the most common cause of an increased steam
contamination. Foaming due to contamination of boiler water, sudden change in pressure
or load are typical disturbances.
The chemical carry-over is due to the solubility of water-soluble solids in steam. The
solubility in steam is primarily dependent on density of steam. As density of steam rise with
pressure and fall with temperature, will the solubility follow the same pattern. The highest
solubility at a given pressure is in saturated steam. Dissolved solids in steam can therefore
precipitate in super-heaters because of density decrease due to temperature rise and on
turbine blades because of density decrease due to pressure drop. The deposits - where
electrolytes are involved -cause corrosion in the presence of water or as a molten material.
Commonly observed corrosion at the place of early condensation at the last turbine rows is
connected with deposition of contaminants decreasing pH of early condensate. Effect of
weak acidic contaminants is therefore moderated comparing to strong acidic contaminants.
The effect may be even more moderated by condensing alkalising agent.
Non electrolytic deposits (i.e. silica) may change the roughness of turbine blades resulting
in decrease of turbine efficiency.

9.2.3 Corrosion

[Link] General
Corrosion is the interaction between a material and its environment. Many different types
of corrosion occur in steam water cycles. The mechanisms and the influence of material
properties, chemical and operational conditions and system design on the corrosion
processes are known today.
Avoidance of corrosion processes and its impact on plant availability and costs should be a
main target of a plant management. This includes an optimized chemical treatment of the
cycles according to this guideline as well.
 53

[Link] Oxygen corrosion/idle corrosion

Damages due to oxygen corrosion are often a result of missing or inadequate lay-up
measures during shutdown periods. Systems or components filled with aerated water or
left drained with moisture and air in it suffer from this type of corrosion. Pits from oxygen
corrosion may act as start location for stress corrosion cracking.
Oxygen corrosion is also a known trouble with the operation of condensate return lines
including atmospheric open condensate collecting tanks or basins.

[Link] Acid corrosion

Acid corrosion results in an uniform removal of the protective layer and attack on the metal.
This process requires concentration of an acidic contaminant, which source may be
condenser leakages, regeneration chemicals or the boiler water treatment with
phosphates. Most commonly the damage occurs in regions with high heat flux, excessive
deposits and/or flow disturbances.
Acid attack on system materials during acid cleaning can be excluded, if standard
practices for chemical cleaning are used [7].

[Link] Caustic Corrosion

Caustic corrosion (caustic gouging) during operation shows the same effect and needs
similar preconditions as the acid corrosion, but with the localized concentration of sodium
hydroxide, e. g. from caustic treatment of the boiler water.

[Link] Hydrogen Corrosion

This type of corrosion requires the liberation of atomic hydrogen, which may occur under
acid corrosion processes. Atomic hydrogen diffuses into the steel, reacts to molecular
hydrogen and/or methane and results in formation of cracks and damage.

[Link] Stress Corrosion Cracking

Stress corrosion cracking is probable, if metal with sufficiently high tensile stresses, prone
to this type of corrosion and a specific corrodent are present. Typical corrodents are
sodium hydroxide for carbon steel and sodium hydroxide and chloride for stainless steel.

[Link] Flow-Accelerated Corrosion

Flow-accelerated corrosion prevents the building-up of protective layers on carbon steel.
The process is influenced by velocity, geometry, temperature, steam quality, water
chemistry and material. The resistance increases with chromium, copper, and
molybdenum content of the material. The maximum of this corrosion attack occurs around
150° C. Beyond approx. 250° C or a pH-value of > 9.5 an attack is unlikely. Oxygen in high
purity water prevents flow-accelerated corrosion.

[Link] Corrosion Fatigue

The causes for corrosion fatigue cracking are cyclic stresses/strains of sufficient order,
produced by pressure fluctuations and/or by rapid temperature changes. Frequent start-
ups and shutdowns promote the start and growth of cracks until penetration or rupture of
the metal.
54

9.3 Economical considerations

Evaluation of economical consequences of operation outside the recommended range is
an extremely difficult task. Even after decades and decades operation experience it was
not possible to estimate the standard costs of operation and maintenance associated to
chemistry, because of great variations of boundary conditions and difficulties in estimation
of the chemical share in long term wear and damages. However, some guide is required to
be able to manage the operation outside the chemically optimal range on an economically
convenient way. Up to date time limits are used for each exceeding of an Action level. But
this system has no relation to the economy, as the price of power varies with time in the
open marked, the price of an alternative production varies as well and remaining value of
the unit varies from place to place. The true economical evaluation is only possible if we
are able to express the life time consumption as a function of operational chemical
parameters. And this is the difficult part of the task. The first attempt is based on quality
index expressing the life time consumption factor relative to reference lifetime consumption
(normal operation). There is no doubt that system will need some adjustments to make
more convenient application possible.

9.3.1 Assessment of water/steam chemistry by quality indices

The quality index I for any control parameter p is in general terms defined as a ratio of
lifetime consumption (TP) of a component effected by the control parameter at the actual
operating value and the lifetime consumption (TL1p) of this component operating at the
reference conditions, which means at the limit between target and action level 1 (L1p).
Ip = dTP / dTL1p (9.3.1)
The index expresses the relative rate of lifetime consumption and will then be 1 at the
operation at the limit for Action level 1, which is considered as conditions with reference life
time consumption:
At P = L1p Ip = I0 = dTL1p/dTL1p = 1 (9.3.2)
The lifetime consumption at actual conditions Tp of a particular component during any
operation period t is then calculated from the formula:
t
Tp = Ip dt (9.3.3)
0

Operating at action level 1 (P > LL1p) the index will have value above 1 and operating
below the action level 1 limit (target area), the index will have value less then 1. Thus the
lifetime consumption will be faster or slower comparing to the operation at reference
conditions.
It is extremely difficult to establish a scientifically or statistically based model for the lifetime
consumption deviations from reference conditions. A pragmatic way was chosen , based
on the following concept:
− The lifetime consumption should be evaluated separately for each main component of
water/steam circuit using parameters significant for component in question.
− The rate of lifetime consumption (Index I) is an exponential function of the relevant
parameter.
− The exponential function is normalized for action level limits defining:
At P = L1p I= 1 (9.3.4)
 55

At P = L2p I= 10 (9.3.5)
At P = L3p I= 100 (9.3.6)
At P = 3*L3p I= 1000 (9.3.7)
The justification of these values is based on some experience from units operating with
good chemical practice and also from units where less attention is paid to chemistry;
however, the data basis is limited.
The index is mathematically related to action levels by the following equations:
P - L1
L2 - L1
Ip = 10 for P < L2 (9.3.8)
P - L2
L3 - L2+1
Ip = 10 for L2 < P < L3 (9.3.9)
P - L3
2 ⋅ L3 +2
Ip = 10 for P > L3 (9.3.10)

where IP is the index for parameter p

P is the monitored value of parameter p
L1 is the threshold for action level 1
L2 is the threshold for action level 2
L3 is the threshold for action level 3
The index can be used for relative evaluation of the chemical performance with respect to
the lifetime consumption of components for which the parameter p is the key parameter. It
has to be emphasized, that it is an evaluation relative to reference conditions and if more
than one key parameter is relevant for the component in question, a combination of indices
as described should be used.

9.3.2 Operation above Action level 3

If the chemistry in an operating unit come out of control and a key parameter exceed the
Action level 3, a continued operation will result in damage. An assessment based on the
system described in paragraph 9.3.1 of a continued operation of an unit with once through
boiler is shown in Figure 11. It illustrates the lifetime consumption for every hour
operation with acid conductivity of feed water in between 1 and 500 µS/cm. Operation time
to expect collapse is also indicated. This is an example only and uncertainty of the
evaluation is quite big. However, it illustrates the order of magnitude of damage.
56

1000000 1000
Equivalent lifetime consumption (h).

100000

Operating time to collaps (h).

100
10000

1000 10

100
1
10

1 0
10 100 200 300 400 500

Acid conductivity in feed water of once through boiler (µS/cm)

Figure 11: Example of lifetime consumption at operation above Action level 3 limit.
 57

10 Bibliography

[1] DIN EN 12952-12, Ausgabe:2003-12, Wasserrohrkessel und Anlagenkomponenten - Teil 12: Anforderungen an die
Speisewasser- und Kesselwasserqualität; Deutsche Fassung EN 12952-12:2003
[2] BS EN 12952-12, Edition: 2003-10-03, Water Tube Boilers and Plant Components – Demands on Feed Water and
Boiler Water Quality
[3] International Electrotechnical Commission (IEC) Technical Specification TS 61370 "Steam turbines - steam purity",
Ed. 1.0 b:2002 ([Link]
[4] VGB Instruction Sheet M 407 G “Conception, Specification and Efficiency Statement for Water Demineralization
Plants. VGB PowerTech Service GmbH, Essen.
[5] VGB Instruction Sheet M 412 L “Tasks and Methods of Condensate Polishing”. VGB PowerTech Service GmbH,
Essen.
[6] VGB Instruction Sheet M 418 Le “Organic Matter and Dissiolved Carbon Dioxide in the Steam Water Circuit of
Power Plant”. VGB PowerTech Service GmbH, Essen.
[7] VGB Guideline R 513 e “Internal Cleaning of Water-Tube Steam Generating Plants and Associated Pipe-Work”.
VGB PowerTech Service GmbH, Essen.
[8] VGB Guideline R 116 He “Preservation of Power Plant Systems”. VGB PowerTech Service GmbH, Essen.