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and
Chemical guidelines for water/steam
cycle of fossil fired units
............................................................................................
............................................................................................
Geoff Bignold (GB), Stefano Concari (IT), Karol Daucik (DK), Geoff
Fitchett (GB), Richard Harries (GB), Giuliano Magnani (IT), Giovanni
Quadri, (IT), Roger Roofthooft, (BE), Andre Zeijseink, (NLs)
Copyright ©
Union of the Electricity Industry - EURELECTRIC, 2000
All rights reserved
Printed at EURELECTRIC, Brussels (Belgium)
TABLE OF CONTENTS
The guidelines are based on the data assembled from the inquiry. As the practice in single countries is adapted
to the local conditions (type of the installation, operation mode etc.), it was necessary to make the guidelines
applicable to the broadest possible range of units used by utilities in UNIPEDE countries. Furthermore, the
guidelines have in view the present and the near future developments of the design, operation and control of
power plants. In particular, two directions have been considered during development of the guidelines. The
introduction of units operating at higher and higher pressure and temperature and introduction of combined
cycle units operating at several pressure stages, where the low pressure stage is operating at unusually low
pressure. Thus, the pressure range is extended in both directions.
Chemical control of water steam cycle based on the concept of action levels was originally been introduced by
nuclear power utilities. The concept was introduced for the first time for fossil fired plants by EPRI. Several
countries around the world, among them some of the UNIPEDE members, adopted the concept because of its
detailed guidance of operators during chemical disturbances of the cycle. However, the definitions of action
levels have to be adjusted when transforming the concept from the application on nuclear power plants to the
application on fossil plants. The safety considerations on nuclear plants demand very rigid application of the
action level concept, while on fossil plants it is more or less a question of an economic assessment. The length
of time a fossil fired plant should be allowed to operate at a certain action level is a question of cost-benefit
evaluation.
The concept of action levels is introduced in the UNIPEDE Guidelines, but some important adjustments are
made to the concept used by nuclear utilities, as well as to the concept introduced by EPRI for fossil fired
plants.
Three action levels and a target for normal operation are defined. Definitions of action levels are slightly
different from the EPRI definitions. A characterisation of each action level is given with an indication of the
risk connected to operation at these conditions. Furthermore, guidance is given for actions whenever an action
level is reached during operation.
The same action levels are recommended for start-up procedure. In this case the unit is in action level 3 region
before start-up. Guidance is given for procedure steps during start-up according to a successive purification of
the cycle and adjustment of parameters.
The UNIPEDE guidelines distinguish between 2 types of chemical parameters - key parameters and diagnostic
parameters. Key parameters are basically purity parameters which should be continuously monitored, if
possible, whereas diagnostic parameters are measured according to operational needs. The most important
difference between parameters is reflected at action level 3, where key parameters call for a forced shut-down of
the unit. The diagnostic parameters call for less radical actions such as load reduction.
Almost all the parameters are specified in diagrams, where the interdependency of parameters is defined. In
some cases it is the interdependency of two chemical parameters (such as pH and oxygen concentration in feed-
water), in others it is dependency of a chemical parameter on full load operating pressure (such as acid
conductivity). In these cases, other parameters, such as heat flux, would be more correct to use, though
extremely inconvenient. There is a certain functionality between the correct parameters and pressure, thus the
most convenient parameter is chosen.
For a successfull implementation of the guidelines, a close cooperation between station chemist and operators,
as well as support from the management, is essential.
i
GLOSSARY
Acid conductivity Conductivity measured after exchange of cations to H+ passing an acid regenerated
cation exchanger. Thus, alkalinity is neutralised and all salts are converted to acids.
AVT All Volatile Treatment. Conditioning concept, where ammonia is used with or
without addition of hydrazine as oxygen scavenger.
CWT Combined Water Treatment (in this document called Oxygenated Treatment, OT).
Conditioning concept, where ammonia and oxygen are added. Very high purity of
water is required for succesful application of this concept.
Equivalent Lifetime Operation time at reference conditions causing the same wear or damage as real
operation time at actual conditions.
Quality Index Index expressing rate of lifetime consumption relative to lifetime consumption at
reference conditions
Strong Mineral Acids Sum of chlorides and sulphates expressed as mg chlorides / kg water.
ii
1. INTRODUCTION
1.1 Overview
The approach adopted has been to encompass all of the national and company reference guidelines for the
chemical control of large generating plant available from the utilities represented in UNIPEDE. These
guidelines have been developed and defined taking account of both operational experience and the
recommendations of the plant suppliers.
The concept of action levels for important chemical control parameters has been adopted, and a procedure for
further development of the use of these in terms of plant lifetime assessment is suggested. In some of the
national and company guidelines action levels are already identified for some parameters for the out of
specification operation of the water, steam circuit. These set out, in broad terms, the time limits for operation
out of specification. In general the action level approach is not supported by the plant suppliers who tend to
specify normal operating parameters only. In Europe the VGB recommendations[2], which apply to industrial
plants in addition to power systems carry international authority.
The concept of action levels has also been adopted by the Electrical Power Research Institute (EPRI) in the
USA[3]; these are probably the most widely adopted guidelines world wide.
The UNIPEDE guidelines will only address fossil fuelled power plants. The action level approach adopted
covers chemical control parameters from normal acceptable operation, through minor perturbations, to more
serious deviations and ultimately plant shut down. Control parameters are chosen as those which are directly
influenceable by operator intervention.
Guidelines from several countries/utilities have been collected together and compared. Only the most
significant chemical parameters for feed-water, boiler water, and steam have been considered, and although a
few UNIPEDE members already use the action level approach, the normal operating values in individual
guidelines have been found to be quite similar (see Appendix 1). It has therefore proved feasible to propose
action levels which are broadly applicable across UNIPEDE members.
Data from the inquiry relate to high pressure plants, including both once through and drum type boilers. The
following operational regimes are covered:
- All volatile treatment, AVT, - reducing regimes in which pH is controlled with ammonia and an
oxygen scavenger (usually hydrazine) may be added.
- Combined water treatment, CWT, or oxygenated treatment, OT, - ammonia under slightly oxidising
conditions usually achieved by oxygen dosing with very restrictive limits on acid conductivity.
(In these guidelines the acronym OT will be used.)
1
- Non-volatile alkali - sodium hydroxide or sodium phosphate boiler water treatment applied under
reducing conditions. (This regime is limited to drum boiler circuits only and ammonia is still used to
adjust pH in feed-water and steam).
All the plants operate with high purity water and steam conditions and almost all national and company
guidelines define the target parameter values to be aimed for (either below or within which to operate) and the
maximum values (or the maximum range) not to be exceeded.
The individual guidelines are based largely on the experience gained in the last twenty years as a result of many
earlier plant failures resulting from inadequate control of water and steam purity.
These guidelines are intended for the operation of fossil fired generating plants. They do not cover low
rated industrial equipment, that operate with softened water. They include multi-pressure combined cycle
plants, where each stage is considered as an individual boiler with respect to limits, but the control strategy
have to take account the interdependency of stages.
Existing guidance, reflecting good practice, takes into account avoidance of corrosion and deposition within
power plant components. In specifying action levels an attempt is made to relate deviation from good practice
to possible plant damage.
- Plant chemistry provides the manager with information for decision making. Commitment of
management, to make economic and safety decisions based on risk assessment, backed by high quality
technical guidance, is essential.
- Action levels must be credible to those running the plant, and making operational decisions, not just
those with specialist chemistry knowledge.
- Operators are normally opposed to shutting-down plant as a consequence of loss of chemical control.
The guidelines recommend conditions for both continuous operation and for plant start-up. A target range and
three levels of action are defined in simple terms below, and in more detail in table 1.
Target range, no action required; this range covers the practicable values which plant managers will
normally achieve without excessive cost.
Action level 2, serious disturbance in chemical control requiring diagnosis and action to eliminate the
cause.
Action level 3, very serious disturbance requiring substantial operator intervention, such as load
reduction, or plant shut-down.
The limits are the same for start-up and continuous operation. For start-up however, the action levels should be
used for optimising the start-up procedure.
2
2. BASICS OF DEPOSITION AND CORROSION PROTECTION
The objectives of chemical control of the water/steam circuit are to minimise corrosion damage and deposition
on the internal surfaces of water/steam circuit as far as is economically prudent:
- Control of redox potential to stabilise oxide films and to minimise transport of metal oxides (usually
pracised by control of oxygen).
- Control of the pH to counter corrosion effects, to stabilise oxide films and to minimise transport of
metal oxides.
Other major influences on the corrosion/deposition process include plant operating history, heat flux and the
impact of phase transitions.
Control of the corrosion and deposition processes are considered for the following areas of plant:
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. 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 bolier 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.
3
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.
2.3 Boiler
- Once through boilers in which water is evaporated to a high steam content. These are not tolerant of
nonvolatile dosing chemicals and generally operate without further dosing downward the feedwater
chemical dosing.
- Drum boilers in which steam separation takes place in an unheated vessel. Boiling occurs in tubes
through which water from the drum is recirculated, preventing dryout 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. During initial operation or post chemical cleaning, 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.
Boiler integrity can be prejudiced by a number of corrosion mechanisms or by overheating due to excessive
thickness of oxide layers.
Nonvolatile impurities can 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.
4
- If strong alkalis concentrate at surfaces, corrosion at unacceptable rates can also occur. Hydrogen
damage is not normally caused by this type of attack, 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 involatile 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.
No direct conditioning of steam is normally applied, and hence the chemical quality of steam derives
from the measures applied to control feed and boiler water. Thus, one of the objectives of feed-water and boiler
water conditioning is to avoid deposition and corrosion in the steam pipework and turbine.
- The concentration and solubility of salts in steam. The solubility is a function of pressure, temperature
and of other chemical components
Sodium hydroxide, hydrogen sulphates and chlorides at certain concentrations present a stress corrosion
cracking risk to steels, particularly with austenitic structures.
Salts deposited in steam pipework on-load can result in the development of concentrated solutions off-load
following condensation of residual steam. This effect is particularly significant for reheaters and some types of
feedheaters.
Decomposition products of organic impurities (organic and carbonate anions) may be implicated in turbine
damage.
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.
Silica is the most soluble of the common boiler water contaminants in high pressure steam and 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.
The chemical control is based on specifications of target and 3 action levels for out of target
concentrations of chemical species. The most significant parameters are defined as key parameters and
stringent control of them is required. If possible continuous monitoring must be applied.
Other chemical measurements will frequently provide valuable diagnostic data. Laboratory support is required
for periodical extended analysis and check of monitors.
5
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 1.
Action levels are time related and the combination of concentration and time are set to minimise damage to
feed water systems, 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.
- Operation in action level 1 regularly requires extended analysis for diagnostic and optimisation
purpose.
- Operation in action level 2 requires qualified interpretation of laboratory and monitor data to enable
the operators to take appropriate corrective steps.
- Operation in action level 3 with respect to the key parameters requires immediate action to shut-down
the unit. In cases when less critical parameters (i.e. results of diagnostic measurements) exceed action
level 3, load reduction will generally be required until the fault is rectified.
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.
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.
Some designs of once-through boilers, with water filled level holding vessel having drain facilities, approach
the conditions of drum boiler (though without moisture separators) during low load operation.
The key parameters for action level 3 decisions are set out in table II.
Table III summarises the specifications of chemical control parameters. Most of these are detailed in the
diagrams in chapter 7, with parameters characterising the purity of the system expressed as function of
operating pressure.
Purity specifications for feed-water at the economizer inlet and for steam are the same, as no
distinction is drawn between units with drums and those with once-through boilers. Operation with condenser
leakage on a drum boiler unit without a condensate polishing plant (CPP) is considered as operation at
particular action level.
The specification of pH and oxygen concentration in feed-water is given as a broad range for information in
figure 1 and 2 (for systems with and without copper alloys). This specification does not suggest random
operation within this range, but identifies the limit at which action level 3 becomes applicable.
6
To find a suitable target operational feed-water pH and oxygen range for a particular unit it is necessary to
optimize conditions for this unit according to its design, materials of construction, operation mode and achie-
vable purity of the water/steam cycle. Particularly when copper alloys are used in the water/steam circuit, the
optimisation must take into account the enhancement of copper oxide solubility in the presence of higher levels
of oxygen and ammonia. Having determined the optimum operational pH, the target operating range is defined
as within ± 0.2 of this value, action level 1 is defined as within ± 0.4 and action level 2 is defined as within ±
1. Limits for oxygen are station specific and are thus individually estimated. Generally the purer feed-water is,
the more relaxed specifications on oxygen can be accepted.
Boiler water pH of drum boilers operating on AVT treatment is determined by the pH of feed-water. A careful
control of low limits in feed-water pH is therefore essential (specified in table III).
Control of pH of feed-water (and hence of steam) may be based on direct conductivity measurements as a
convenient reliable alternative for many plants.
Figure 3 specifies the action levels for acid conductivity of steam and feed-water.
Figure 4 shows action level limits for sodium in steam. For once through boilers this limits apply to
superheated steam as well as to feed-water. For drum boilers this applies to saturated steam.
For boiler water, the action levels for units with drum boilers vary depending upon whether the
applied treatment is AVT or non-volatile alkali. Because of the enhanced ability of sodium hydroxide and
phosphate dosed systems to maintain alkaline conditions at the boiler tube surface, greater concentrations of
impurities than under AVT conditioning are tolerable in the bulk water and this is reflected in a higher
acceptable acid conductivity.
Action levels and target ranges for boiler water pH are given in figure 5 . The figure expresses the dependence
of the high and low pH limits on the pressure of the boiler and on the acid conductivity of boiler water. The
optimal pH of boiler water increases with increase of acid conductivity, but falls with increasing pressure. The
ratio of acid conductivity to boiler pressure can be used to derive specific pH limits for any individual boiler.
Some examples of this procedure are shown in Appendix 2.
The broad range of normal operation is for general guidance only. The normal range of operation for a given
unit is dependent upon the chosen chemical conditioning regime and on factors specific to that unit.
Boiler water pH for AVT dosed plant is determined by feed-water treatment. The control of feed-water pH is
thus essential not only for condensate and feed-water circuit, but also for the boiler. Because of the high
volatility of ammonia, the pH of boiler water is considerably lower than the pH of feed-water. Particularly at
low pressure a very high ammonia concentration is necessary to reach sufficient high pH in boiler water.
Therefore, AVT treatment of boilers below 8MPa, particularly those with copper alloy components in the
condenser and/or feedwater circuit, is not recommended.
The control of boiler water pH in units conditioned with sodium hydroxide is usually based on the measurement
of conductivity and acid conductivity. These two parameters give the operator a safe and reliable method to
controlling boiler water purity by blow down and pH by either dosing additional NaOH or blowing down the
excess.
Boiler water pH in units alkalized with a phosphate is controlled by direct measurement of pH and phosphate.
On units where phosphate hide-out occurs, a measurement of sodium is also necessary to assure adequate
controll.
Guideline concentrations for the most important impurities in boiler water are given in figures 6, 7 and 8. The
anionic impurities are controlled via acid conductivity measurements of boiler water, when AVT or sodium
hydroxide is used for pH control. When phosphate treatment is chosen for pH control, this measurement would
be disturbed by phosphate contribution to the acid conductivity. Limits for concentration of strong mineral
7
acids (fig. 9) are then used to ensure purity of boiler water. The practical definition of strong mineral acid
concentration is the sum of chloride and sulphate concentrations.
4.3 Condensate
Because condenser leakage is the major source of impurities in circuits, monitoring of the 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.).
Units with once through boiler are always equipped with a condensate polishing plant (CPP) to take care of this
problem. The CPP should be designed, maintained and operated on a standard which is able to cope with
condenser leakages.
Drum boiler units often do not have a CPP and in case of condenser leakage precautions must be taken to avoid
damage.
The specific action level responses (action level determined by feed-water specifications) appropriate to
contamination of condensate are as follows:
Action level 1 - reduce flow to attemporators sufficiently to maintain sodium in steam within target. This may
imply either feeding attemporators from an uncontaminated alternative source, or minor load reduction in order
to avoid overheating.
Action level 2 - terminate flow to attemporators. Adjust load and provide alternative uncontaminated water
source as appropriate. Prepare to increase boiler blow-down or condensate polisher regeneration frequency
(where fitted). Plan to address condenser leakage at first convenient opportunity.
Action level 3 - reduce load and address condenser leakage as soon as practicable.
5. FUTURE DEVELOPMENTS
The action level concept is seen as positive progress towards the development of optimal control
routines. Operation outside the target region will cause damage and its impact will depend on both the size and
the duration of the excursion. EPRI has addressed this relationship, giving time limits for operation at each
action level during one year. This is a rather rigid approach, and does not take into consideration the actual
operating conditions and lifetime prognosis for the installation. A system of chemistry evaluation on the basis
of economic/scientific evaluation of all possibilities for damage is not possible. A somewhat more pragmatic
system based on quality indices is suggested in Appendix 3 of these guidelines. This system is based on a
simple mathematical presentation of general long time operational experience. However, it must be considered
as a rough preliminary guide and may benefit from future development.
6. REFERENCES
[1] Report on the chemical standards of the water-steam cycle in Power Stations as in use by the member-
Countries of the UNIPEDE. KEMA, Arnhem, november 1970. Made for UNIPEDE SUB-
COMMITTEE for the study of electric Power Station Chemistry.
[2] VGB-R 450 L - Richtlinien für Kesselspeisewasser, Kesselwasser und Dampf von Dampferzeugern
über 68 bar zulässigem Betriebsdruck, 1988
[3] Interim Consensus Guidelines on Fossil Plant Cycle Chemistry, EPRI CS-4629, June 1986
8
7. TABLES
9
TABLE I. Definitions and characteristic of Action Levels
Target Normal stable operation, The maintenance of chemical control through the Target should be reached within 24 hours. If not,
where everything is monitoring of key parameters should be continued. improvements in system control are required.
under control
1 Periodic or minor Long term damage and Monitoring of the circuit chemistry should be Action level 1 for key parameters should be achieved in 2
disturbances in chemical reduction in remaining extended to diagnostic components to identify the to 8 hours for warm and cold starts respectively.
control. life of power cycle source of the problem. Strategic considerations
components. should be made to avoid similar occurrences in the
future.
2 Serious loss of chemical Serious damage to Immediate action should be taken to find and Fire the boiler. Check the steam quality. At least action
control. components due to eliminate the cause within hours and/or actions level 2 for all parameters should be reached before
deposition and should be taken to minimise the damage (e.g. turbine is brought into service.
corrosion. Significant decrease load).
reduction in the
component life
3 Chemistry out of Component failure. The unit should be shut down within 1 hour using Purge the boiler until all the key parameters are below
control. the normal shut down procedure if one of the key action level 3.
parameters deteriorate to action level 3. If one of the
diagnostic parameters deteriorates to this action
level, reduce load to prevent immediate damage and
to gain time to restore chemical control.
10
TABLE II. Key parameters for control of water/steam cycle
Oxygen Fig. 1, 2
(µg/kg)
Silica 10 20 50 Fig. 8
(µg/kg)
Sodium Fig. 4
(µg/kg)
Iron 5 20 100
(µg/kg)
11
Figure 1
pH and Oxygen in Feed-water
Copperfree circuit
200
O2 (µg/ l)
100
0
8 9 10
pH
12
Figure 2
pH and Oxygen in Feed-water
Copper a lloys present
200
O2 (µg/l)
100
0
8 9 10
pH
13
Figure 3
Feed-water and Steam
Action Levels for Acid Conductivity
10
0,1
0,01
0 5 10 15 20 25 30
Pressure (MPa)
14
Figure 4
Feed-water and Steam
Action Levels for Sodium
1000
100
10
0,1
0 5 10 15 20 25 30
Pressure (MPa)
15
Fig. 5
Boiler Water - Solid Alkaliser
Action Levels for pH
1000
100
10
0,1
0,01
7,00 7,50 8,00 8,50 9,00 9,50 10,00 10,50 11,00 11,50
pH
16
Figure 6
Boiler Water treated with NaOH
Action Levels for Acid Conductivity
1000
100
10
1
0 2 4 6 8 10 12 14 16 18 20
Pressure (MPa)
17
Figure 7
Boiler Water - AVT
Action Levels for Acid Conductivity
100
10
0,1
0 2 4 6 8 10 12 14 16 18 20
Pressure (MPa)
18
Figure 8
Boiled Water
Action Levels for silica
100
10
0,1
0,01
0 2 4 6 8 10 12 14 16 18 20
Pressure (MPa)
19
Figure 9
Boiler Water treated with phosphate
Action Levels for Mineral Acids
10
0,1
0 2 4 6 8 10 12 14 16 18 20
P ressure (MPa)
20
Appendix 1
Comparison of significant parameters for control of water/steam cycle in UNIPEDE countries
21
A 1 - TABLE I. Comparison of Significant Parameters for Feed Water of Drum and Once Through Boilers (AVT)
Country BE DE DK ES FI FR GB IE IL IT NL PL PT SE
Acid Conduc- N <0,2 0,1 <0,1 <0,2 <0,2 0,1 <0,1 <0,09 0,1 <0,15 <0,2 0,1 <0,2 <0,2
>0,2 >0,15 >0,2 >0,12 >0,2 <0,2 >0,2
tivity 1 >0,18 >0,2 >0,35
2 >0,30 >0,65
(µS/cm) 3 >2
pH N 9,2-9,5 9 - 10 9,2-9,4 9-10 9,0-9,2 9,1-9,3 8,8-9,2 9,2-9,6 8,8-9,4 9,1-9,2 9,0-9,2 9,1-9,3 9,0-9,3 8,5-9,2
9 -9,4 <9,2 9,0-9,3
1 <8,7
2 <8,0
3
O2 N <10 < 100 < 10 <7 <10 <5 <5 <7 2-5 <5 <5 <20 <7 <10
<10 <10 >7 >7
1 >15 >10
(µg/kg) 2 >50 >20
3
22
A1 - TABLE II. Comparison of Significant Parameters for Feed Water at OT of Once Through Boilers
Country BE DE DK ES FI FR GB IE IL IT NL PL PT SE
N2 H4 N
1
(µg/kg) 2
3
23
A 1 - TABLE III. Comparison of Significant Parameters for Boiler Water of Drum Boilers on Solid Alkalizer (16 MPa)
Country BE DE DK ES FI FR GB IE IL IT NL PL PT SE FI
(mg/kg) <3 - 1-4 2-6 1,5.NaCl 0,5-1,5 3-5 1-6 2-6 2-6
Acid Conduc- N < 50 < 15 150* <15* < 3 15-23 * < 60* <132 * <150 *
< 10
tivity 1 < 20
2 <100 > 20
(µS/cm) 3
SiO2 N < 200 < 250 350 < 200 < 200 20-100 <400 <350
< 400
1 < 800 < 400
(µg/kg) 2 > 800
3
24
A 1 - TABLE IV. Comparison of Significant Parameters for Boiler Water of Drum Boilers on AVT (16 MPa)
Country BE DE DK ES FI FR GB IE IL IT NL PL PT SE
Cl- N
1
(µg/kg) 2
3
25
A 1 - TABLE V. Comparison of Significant Parameters for Steam
Country BE DE DK ES FI FR GB IE IL IT NL PL PT SE
Acid Conduc- N <0,2 0,1 <0,1 <0,2 < 0,2 0,1 <0,1 0,1 <0,15 <0,2 <0,25 <0,2 <0,2
tivity 1 0,2 0,15 <0,2 0,15 <0,2 >0,20 >0,2
2 0,20 >0,3
(µS/cm) 3 > 0,5 > 0,5 0,30 >0,5
SiO2 N <15 5 < 20 <10 <20 <20 <20 <5 <10 <20 <20 <20 <20
1 < 20 <10
(µg/kg) 2 <20
3 >20
Na+ N <5 2 <3 <10 <2 <2 <5 <3 <1 <10 <10
1 < 10 (<5) <5
(µg/kg) 2 <10
3 >10
(µg/kg) <3
26
Appendix 2
Examples of Action Level Limits for pH of boiler water at different pressures
27
A2 Figure 1
0.5 MPa - Boiler Water treated with solid a lka liser
Action Levels for pH
1000
100
Acid Condutivity (µS/cm)
10
0,1
7,00 7,50 8,00 8,50 9,00 9,50 10,00 10,50 11,00 11,50
pH
28
A2 Figure 2
2 MPa - Boiler Water treated with solid alkaliser
Action Levels for pH
1000
100
10
0,1
7,00 7,50 8,00 8,50 9,00 9,50 10,00 10,50 11,00 11,50
pH
29
A2 Figure 3
8 MPa - Boiler Water treated with solid a lka liser
Action Levels for pH
1000
100
Acid Conductivity (µS/cm)
10
0,1
7,00 7,50 8,00 8,50 9,00 9,50 10,00 10,50 11,00 11,50
pH
30
A2 Figure 4
16 MPa - Boiler Water treated with solid alkaliser
Action Levels for pH
100
10
0,1
7,00 7,50 8,00 8,50 9,00 9,50 10,00 10,50 11,00
pH
31
Appendix 3
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 (T L1p) of this component operating at the reference conditions, which means at the limit between
target and action level 1 (L 1p).
Ip = dTP / dTL1p
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 lifetime consumption:
At P = L1p Ip = I0 = dTL1p/dTL1p = 1
The lifetime consumption at actual conditions T p of a particular component during any operation period t is
then calculated from the formula:
TP = ∫I
0
P * dt
Operating at action level 1 (P > L L1p and P < L L2p) 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 the componen t in question.
- The rate of lifetime consumption (Index I) is an exponential function of the relevent parameter
- The exponential function is normalized for action level limits defining:
at P = L1p I= 1
at P = L2p I = 10
at P = L3p I = 100
at P = 3*L3p I = 1000
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.
P − L1
L2 − L1
I P = 10 for L1 < P ≤ L2
P − L2
+ 1
L3 − L2
I P = 10 for L2 < P < L3
32
P − L3
+ 2
I P = 10 2* L3
for P > L3
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 described on page 33 should be used.
For a typical cold start-up a good practice is to reach L1 (coming from L3) for acid conductivity in feed-water
within 24 hours. The calculation shows, that the mean value of the index I is about 30. This indicates, that the
chemical load on the evaporator during this day of start-up is similar to the load of 30 (720 h) days of operation
at L1. For a unit, which is not performing very well, the purification period during the start-up can easily take 2
days, which makes the life consumption for the whole period 2*30=60 days (1440 h).
Similarly it can be calculated, that a hot start-up of a good unit taking 16 hours will be equivalent to roughly
200 h lifetime consumption, while unattended unit will use 400 h equivalent operation at reference condition.
Table A 3.1 shows some examples of units with different operation mode (1. base load, 2. cycling load, 3. peak
load) and different quality of chemical control (A. Ideal purity, B.Good practice, C. Unattended control). In
the following the layout and calculation procedure are explaned:
33
I=
∑ I *t
i i
=
0,501 * 3000 + 1 * 4000
= 0,786
∑t i
3000 + 4000
Column 8 show the calculated equivalent lifetime consumption T c including contributions from start-ups. The
calculation for row 1B is as follows:
The registered lifetime consumption is of course 7000 h, but chemically the evaporator has received more load
due to start-ups, but decreased load because of the excellent purity in part of the operation time. In calculation
of examples with purity standard C, a higher life time consumption is used for start-ups (1440, 400).
Columns 9 and 10 show a prognosis for acid cleanings if the same operating conditions would be maintained
all the time. This calculation is based on experience with units operating close to the conditions of the reference
unit. These units used to be acid cleaned after 100 000 operating hours.
Tables A 3.II - A 3.V show similar exercises for drum boilers on NaOH and AVT respectively. Two key
parameters are used for separate calculation in each case, and in the table A 3.VI a combined evaluation of
indices calculated from these two key parameters is shown. As the best combination of indices was found to be
their sum -1. Mathematically:
I12 = I1 + I2 - 1
More generaly:
i
I 1i = ∑I
i =1
i − i+ 1
On the basis of these combined indices the expected acid cleaning frequency is calculated.
It must be emphasised that the method is designed for evaluation of operational lifetime consumption. The
impact of the off-load damage on lifetime must be evaluated separately. It may be possible to use the same
concept, but a careful consideration should then be given to reference condition, key parameters and action
levels.
34
Table A 3.I Examples of Lifetime Evaluation of Evaporator Protective Layer
Once Trough boiler - Acid conductivity of Feedwater
L1 L2 L3 3*L3
0,1 0,2 0,5 1,5
I 0,501187 1 3,1622777
Ref. 1 5 7000 1 8720 11,5 100000
35
Table A 3.II Examples of Lifetime Evaluation of Evaporator Protective Layer
Drum boiler - Acid conductivity of Boiler water - NaOH treated
Limits L1 L2 L3 3*L3
µS/cm 5 15,8 50 150
I 0,65285 1 2,90378
Ref. 1 5 7000 1 8720 11,5 100000
36
Table A 3.III Examples of Lifetime Evaluation of Evaporator Protective Layer
Drum boiler - pH of Boiler water - NaOH treat.
Limits L1 L2 L3 3*L3
I 1 4,64159 39,8107
37
Table A 3.IV Examples of Lifetime Evaluation of Evaporator Protective Layer
Drum boiler 16 MPa - Acid conductivity of Boiler water - AVT treat.
Limits L1 L2 L3 3*L3
µS/cm 1 2,29 5,23 150
I 0,69978 1 5,95928
38
Table A 3.V Examples of Lifetime Evaluation of Evaporator Protective Layer
Drum boiler 16 MPa - pH of feed-water - AVT treat.
Limits L1 L2 L3 3 * L3
9 8 7 6
I 1 3,16228 31,6228
39
Table A 3.VI Evaluation of drum boiler lifetime consumption on basis of combined Index
Treatment NaOH AVT
Purity pH Combined Used eq. Purity pH Combined Used eq.
Index Index Index lifetime Index Index Index lifetime
I1 I2 I12 (h) I1 I2 I12 (h)
40
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