Steam Purity For Turbine Operation
Steam Purity For Turbine Operation
Steam Purity For Turbine Operation
Contents
1 Nomenclature and Definitions ...................................................................................................3
2 Introduction: Purpose of Document and How to Use it .............................................................5
3 Background ................................................................................................................................7
3.1 Chemical Environment in the Steam Turbine .....................................................................8
3.1.1 Path of Impurities into the Steam .................................................................................8
3.1.2 Nucleation of Early Condensate Droplets ....................................................................8
3.1.3 Formation of Liquid Films on PTZ Surfaces ...............................................................9
3.1.4 Influence of Steam Purity on Early Condensate Nucleation and Liquid Films .........10
3.1.5 Deposition ..................................................................................................................10
3.1.6 Shutdown Environment..............................................................................................12
3.2 Damage Mechanisms in the Steam Turbine ......................................................................12
3.2.1 Deposits ......................................................................................................................12
3.2.2 Corrosion ....................................................................................................................13
4 Guidance to Limit the Effects of Poor Steam Chemistry.........................................................14
4.1 Steam Purity Parameters ...................................................................................................14
4.1.1 Impurities ...................................................................................................................14
4.1.2 Conditioning Agents ..................................................................................................16
4.2 Monitoring Instrumentation ..............................................................................................17
4.3 Layup .................................................................................................................................17
4.4 Mitigating Consequences of Sub-optimum Steam Chemistry ..........................................17
5 Table of Chemistry Limits .......................................................................................................19
5.1 Table of Steam Purity Limits ............................................................................................19
5.1.1 Condensing Turbines with Superheated Steam .........................................................19
5.1.2 Condensing Turbines with Saturated Steam ..............................................................19
5.2 Limits for Normal Operation .............................................................................................19
5.3 Development of Limits for Startup....................................................................................20
5.4 Development of Action Levels ..........................................................................................21
5.5 Development of Shutdown Limits ....................................................................................21
6 Road Map Approach to Customize Steam Purity Limits to Plants with Specific Features .....22
6.1 Turbines for Cycling or Peaking Operation ......................................................................22
6.2 Turbines with Extended Periods of Shutdown ..................................................................23
6.3 Backpressure Turbines ......................................................................................................23
6.4 Turbines for Industry and Process Supply.........................................................................24
6.5 Turbines with Solar and Biomass Steam Generating Systems ..........................................26
6.6 Turbines with Geothermal Steam ......................................................................................26
6.7 Turbines with Steam Generated in Nuclear Power Plants.................................................27
6.8 Ultrasupercritical Turbines with Steam Temperatures above 600 C ...............................29
6.9 Turbines in Plants with Boilers using Phosphate Treatment .............................................29
6.10 Turbines with Steam containing Elevated Levels of Carbon Dioxide ..............................30
6.11 Turbines with Steam containing Organic Decomposition Products..................................30
6.12 Turbines with Steam containing Elevated Levels of Silica ...............................................31
6.13 Turbines in Power Cycles containing Major Components with Copper or Aluminum ....32
7 Bibliography and References ...................................................................................................33
Term
Alternative or
Acronym
Definition
All-volatile
Treatment
AVT
AVT(R)
AVT(O)
Attemperator
Condensate
Conductivity
Specific
Conductivity
Direct
Conductivity
Conductivity after
cation exchange
CACE
Cation
Conductivity
Acid Conductivity
Caustic Treatment
CT
Hydroxide Dosing
Corrosion Fatigue
CF
Degassed
conductivity after
cation exchange
Degassed Cation
Conductivity
Drum boiler or
HRSG (drum-type)
Feedwater
Term
Alternative or
Acronym
Definition
Flow-accelerated
Corrosion
FAC
Heat Recovery
Steam Generator
HRSG
HCF
Ion Chromatography IC
Once-through boiler
or HRSG
Oxygenated
Treatment
OT
ppb, g/kg
ppm, mg/kg
Phase-transition
Zone
PTZ
Pitting
Phosphate
Treatment
PT
Stress Corrosion
Cracking
SCC
Tri-sodium
phosphate
TSP
IAPWS has issued a series of Technical Guidance Documents for the steam cycle
chemistry control of conventional fossil and combined cycle plants.2,3,4,5 The volatile
treatment and phosphate/caustic documents include limits for steam purity. The purpose of
this document is to provide further guidance on the development of steam purity limits to
assist operators of a broader suite of generating plants in minimizing equipment damage
and loss of efficiency, and in maximizing plant reliability. To avoid the major types of
damage in the steam turbines, equal emphasis must be given to the operating as well as to
startup and shutdown environments, and these are discussed within this document. The
guidance can be used directly by chemists and plant operators, and to develop
international, national, company and manufacturers guidelines. It should be noted that the
guidance for feedwater and boiler treatments of conventional and combined cycle/HRSG
plants have been published in other IAPWS Technical Guidance Documents4,5 and the
Normal/Target values for feedwater and boiler water remain the same.
The primary purposes of this document are to: a) highlight the problems which can exist in
steam turbines, b) indicate how these problems occur and can be avoided, c) provide a set
of normal steam purity limits that will provide optimum protection for power plants using
fossil, nuclear, alternative and geothermal energy, including turbines in industrial
applications, and d) provide sufficient discussion that the reader can customize these
normal values to actual plant configurations.
The IAPWS experiences with steam purity are covered within this document, but a number
of initial general principles and comments are delineated here:
a) The success of any steam purity guidance and limits ultimately depends on the
operating experience and the lack of any serious failures, damage and deposits.
Thus the guidance must be linked closely with comprehensive inspections during
shutdown periods. Deposit samples should be carefully taken from each turbine
stage, and analysis results should include elemental, compound and metallurgical
assessments.
b) It is important to note the locations and topography of deposits when they are
removed. In the low pressure (LP) turbine it is important to note both the stage in
relation to the Mollier diagram for expansion and the locations on the blade profile.
5
Any signs of pitting should also be recorded. The locations of deposits in high
pressure (HP) and intermediate pressure (IP) sections should also be noted
carefully.
c) For drum type units, it is of paramount importance that carryover is measured on a
frequent basis according to the IAPWS Technical Guidance Document.2 This is
particularly important when phosphate and NaOH alkalizing chemicals are added to
the boiler/HRSG evaporator water, because elevated carryover can be a major
source of corrosive impurities in the steam. Carryover is a function of drum
pressure and therefore is more important at high steam pressures.2
d) Operators of all units must recognize that attemperation water injected directly into
the steam is often a source of impurities, including oxides/hydroxides from the
feedwater system.
e) The IAPWS solid alkali Guidance Document5 is based on more than 20 years of
excellent experience worldwide using tri-sodium phosphate and NaOH. Use of PT
and CT chemistries outside the dosing limits for phosphate and NaOH additions
will require careful review and modification of the suggested steam purity limits
presented in this document
f) Plant operators must have knowledge of every chemical added to the cycle to
ensure that the correct steam purity limits are selected and applied. The effects of
proprietary chemicals of undisclosed composition and of their decomposition
products must be known.
The development of operating steam purity guidance requires several steps. The starting
point in this document is Section 5.1, which contains the Tables of Normal/Target
chemistry limits. Customization to specific plant conditions or plant types (industrial,
geothermal, nuclear etc.) is done within Section 6.
It is emphasized that this is an IAPWS Technical Guidance Document representing the
cumulative experience of IAPWS PCC Working Group members, and as such should be
regarded as guidance for operating cycle chemistry limits for plants under stable operating
conditions. This guidance is customizable to units that cycle and those that have extensive
shutdown periods. This guidance document can form the basis of, but should not restrict,
other derivative guidelines around the world.
Experience has indicated that the Normal/Target values in Section 5.1 will provide good
reliability and availability if they are customized for each plant to account for actual
conditions of operation, the equipment installed, the materials used at different locations in
the cycle, the chemical treatments, and the condenser cooling media. Customization is
accomplished in two steps. The first step is to develop Action and Shutdown Levels, which
require the plant operator or chemist to take some avoiding or corrective action. The
second step customizes the tables to specific unit conditions, materials, chemistry, and
possible damage mechanisms following the roadmap approach in Section 6.
Background
Impurities in the steam may cause deposits and corrosion in steam turbines that adversely
affect their operation. These problems can usually be avoided by following the guidance in
this document.
The three most important corrosion-related failure mechanisms in any low pressure steam
turbine are pitting, corrosion fatigue and stress corrosion cracking. The local steam
environment determines whether these damage mechanisms occur on blade and disk
surfaces. The phase transition zone (PTZ), where the expansion and cooling of the steam
leads to condensation, is particularly important. A number of processes that take place in
this zone, such as precipitation of chemical compounds from superheated steam,
deposition, evaporation, and drying of liquid films on hot surfaces, lead to the formation of
potentially corrosive surface deposits. Understanding the processes of transport, droplet
nucleation, the formation of liquid films on blade surfaces, and concentration of impurities
is vital to understanding how to avoid corrosion-related damage, and to improve unit
efficiency/capacity.
Over the last 20 years, the understanding of the driving force behind these damage
mechanisms has changed. About 30 years ago, major research concluded that turbine
corrosion mechanisms were driven by high oxygen levels in concentrated solutions
containing extreme levels (up to almost 30%) of chloride, sulfate, and hydroxide.
Recent improved understanding of the turbine environment has identified the following as
significant factors relevant to turbine corrosion:
The dynamic environment during turbine operation. These are the local conditions
formed by the condensation of steam as it expands through the PTZ of the turbine,
and by the deposition of salts, oxides and other contaminants directly onto steam
path surfaces. It has now been shown that there is no oxygen in the liquid films
during operation (i.e., when the damaging stress is applied).
The environment produced during shutdown. These are the conditions that occur
during unprotected shutdown when oxygenated moist/liquid films form on steam
path surfaces as a result of hygroscopic effects. These films are directly caused by
inadequate shutdown practices adopted by the turbine operator. They can lead to
pitting, which is most often the precursor to the corrosion mechanisms.
7
Steam purity and shutdown conditions are only two of the parameters that lead to
the corrosion damage. Adequate materials properties (composition, structure,
internal stresses, etc.) and design (temperature, stresses, crevices, etc.) also play
essential roles.
Thus, if adequate layup protection (dehumidified air) is not guaranteed, serious corrosion
damage may occur even with the best operating chemistry, materials, design, and with only
few major deposits. It is recognized that pitting can possibly also initiate during operation
in crevice areas such as blade attachments.
The purity of turbine steam controls most corrosion processes and is vital to plant
reliability. The goals of developing steam purity guidance are to minimize equipment
damage and loss of efficiency, and to maximize reliability. Additionally, the
recommendations must be practically achievable and incorporate targets that can be
measured by existing monitoring devices.
3.1
As the expansion proceeds through the turbine, the impurity concentrations are diluted as
the droplets add moisture and grow. For drum and once-through/supercritical units, at the
exit of the turbine there is about 7-11 % of moisture depending on the efficiency of the
turbine and cycle. In other plants included in this IAPWS document, the moisture
percentage will be different, but should be known. After the last turbine stage, this mixture
usually flows to a condenser where the associated sub-cooling causes the remaining vapor
to nucleate and condense homogeneously. In industrial plants this mixture might provide
process steam.
3.1.3 Formation of Liquid Films on PTZ Surfaces
Liquid films form on the steam turbine materials as the steam flows through the PTZ.
These films can be up to 100-120 m in thickness,6 and form either by collision of the
liquid droplets or by heterogeneous nucleation on the blade/disk material itself. They may
be subject to reheating due to heat transfer across a turbine disk or shaft and result in
concentration of ionic impurities by up to a factor of about 1000 times the levels found in
bulk steam. In the case of anionic impurities, the pH of the liquid film may have a low or
even acidic pH.
It is important to note that the levels of dissolved oxygen in these liquid films are very low,
usually < 1 g/kg, even when the oxygen levels in the steam are in the hundreds of g/kg.
The low oxygen concentration limits the corrosiveness of anions in the liquid films.
It should also be mentioned that these liquid films flow off the surfaces, break up, and
form droplets up to 100 m in size which is considerably larger than the nucleated early
condensate droplets discussed in the previous section. These larger droplets not only
cause the erosion of blades in downstream turbine stages, but they also can cause liquid
impingement damage (or low temperature FAC) in water- and air-cooled condensers. The
overall flow of the two-phase liquid out of the turbine consists of a large fraction (>90%)
of very small droplets (on the order of 0.1 m) and a smaller fraction (< 10%) of the large
droplets (up to 100 m).
These liquid films play an important role in PTZ failure mechanisms in that both corrosion
fatigue and stress corrosion cracking require an aqueous electrochemical solution for crack
growth to occur during operation. The liquid films that span the PTZ form tortuous paths
across steam path surfaces that are unique to each machine. Thus a number of blade and
diaphragm stages in the PTZ are always touched by these liquid films, and unless
measurements are made with laser probes, the film profiles can only be modeled or
inferred. Sometimes observations of stains and water lines on PTZ surfaces during
inspections can provide information about the operational liquid films.7 The film profiles
certainly include rotor blades and attachment points where cracking and damage take place
in the PTZ. From the standpoint of blade design, it is important to consider wetness
profiles so that an approximation can be made of the moisture percentage at potential
damage locations. The lower the concentration of moisture, the more concentrated are the
harmful anions.
9
It should be mentioned that liquid films are not restricted to the PTZ. Solutions with an
elevated boiling point, such as concentrated solutions of NaOH, may form corrosive liquid
films in the HP or the IP turbine, well within the superheat area of the Mollier diagram.7
When the turbine is shut down, these NaOH films turn white when they are carbonated by
exposure to air. Such films and deposits are usually harmless, but are an important
indicator of carryover and poor operation with NaOH or phosphate treatments. For
susceptible materials however, hot NaOH solutions induce severe corrosion even in the
absence of oxygen (Section 3.2.2).
3.1.4 Influence of Steam Purity on Early Condensate Nucleation and Liquid Films
It is important to emphasize that the formation of droplets and liquid films are natural
processes governed by the thermodynamics of steam expansion. The concentration
mechanisms discussed in this Section occur in all types of steam turbines in generating
situations included in this IAPWS Technical Guidance Document, even on fossil and
combined cycle units with world-class cycle chemistries. In all cases, anions entering a
turbine with steam will concentrate in droplets and liquid films by the multiplication
factors indicated in the previous sub-sections for fossil and combined cycle plants.
3.1.5 Deposition
In parallel with the formation of droplets and liquid films, deposits form on steam-path
surfaces throughout the PTZ, and indeed throughout the other pressure stages of the
turbine. The deposit formation process is complex, involving impaction of crystals of
salts, oxides and other compounds, as well as deposit formation due to thermophysical and
chemical processes such as precipitation from superheated steam, evaporation of moisture,
adsorption of impurities and decrease of compound solubility. Deposition is strongly
influenced by the surface finish of the PTZ blades/disks.
Deposition on these surfaces plays an important role in the dynamic process that can result
in damage and failure. Deposits become moist during periods of non-protected shutdown
and lead to passivity breakdown and pitting which are key parts of every initiating event
for corrosion fatigue and stress corrosion cracking, and often, even for high cycle fatigue
(HCF) on last stage blades.
The most common corrosive deposits are salts of chloride and sulfate. Obviously, the
cleaner the steam, the less deposition occurs; however, an international collaboration in the
1990s10 found that deposits (including salt crystals) can form on any turbine surface during
operation even in fossil and combined cycle units with the best cycle chemistries and
cleanest steam. This finding led to the steam limit of 2 g/kg for sodium in the IAPWS
Technical Guidance Documents covering superheated steam for fossil and combined cycle
plants.4,5 The same limit is also provided for chloride and sulfate, though the continuous
measurement of these parameters is not usually performed and values have not been
included in the IAPWS Instrumentation Guidance Document.3 Thus the intent of the limit
on these deposit-forming species is to minimize deposition on blade/disk surfaces, while
recognizing that some deposition is inevitable in every steam turbine, and to an even
10
greater extent in industrial and geothermal turbines. Further, it is expected that deposition
will be more pronounced on surfaces within the steam flow, and that deposits will form in
crevice areas, such as those between the blade and the steeple. The pits that initiate damage
and failure can form at all of these deposit locations.
The solubility of impurities in steam generally decreases as the steam expands. When the
solubility of an impurity falls below the impuritys concentration in steam, it may
precipitate and form a deposit. Deposits reduce steam passage and steam flow at the
turbine blades, and, when in substantial thickness, impair turbine capacity and efficiency.
Examples of deposits that can form in a steam turbine include salts, copper oxides and
hydroxides, sodium phosphates, silica and sodium silicates, aluminum hydroxides, etc.
Many types of deposits are also corrosive when they become moist.
Deposition throughout the steam turbine can be controlled by keeping the impurity
concentration in steam below its solubility limit. Figure 2 and Figure 3 give examples of
the solubility limits of SiO2 and NaCl under various steam conditions. It is seen that in
order to prevent deposits of pure silica, the SiO2 concentration in steam should be < 10
g/kg, while for NaCl a much lower concentration, on the order of 0.01 g/kg, might
theoretically be required.
The solubility of NaOH is thought to be similar to NaCl, and it is undisputed that the
solubility of Na2SO4 is considerably lower than that of NaCl. Similar information has also
been researched for other substances, but the experimental data deviate such that an error
of up to two orders of magnitude is possible11,12 and therefore no data will be given in this
guidance document.
Such solubility curves are valid only at equilibrium conditions, which are hardly expected
given the rapid steam expansion in the turbine.13 Further, when an impurity does
precipitate from steam, a large fraction of it passes along with the steam as dust and
possible heterogeneous nuclei for the upcoming steam condensation, rather than depositing
on turbine component surfaces. Experience, however, indicates that at least for silica,
Figure 2 is not far from representing in-plant conditions of occurrence and location of the
deposits.14
As mentioned above, cleaner steam yields fewer deposits. Similarly, deposition from steam
with a high concentration of impurity yields thicker deposits than deposition from steam
with a low impurity concentration. In the latter case, the steam holds a lower quantity of
substance that is available for depositing.
Although it would be desirable to have zero deposition in the turbine, this is generally not
practicable. For example, the solubility of sodium chloride in low pressure turbine steam at
0.1 MPa is approximately 0.01 g/kg. Maintaining steam purity at this concentration is
unlikely, but the rate of deposition from higher concentrations, such as 1 g/kg, may be
acceptable. Results from the 1990s International Collaboration Study on fossil-fired utility
power plants10 have indicated that limits of < 2 g/kg for Na, Cl, and SO4 are a reasonable
11
balance between the ideal scenario of zero deposition and actual operating experience and
the relation of cost-to-benefit.
3.1.6 Shutdown Environment
When a plant is not operating, no droplets or liquid films are formed on the PTZ surfaces.
But the deposits formed during prior operation remain on the blade/disk surfaces and in the
blade/steeple crevices. These deposits become of critical importance during shutdown
depending on whether the PTZ is protected. Under non-protected shutdown, steam path
surfaces are exposed to ambient conditions and the deposited crystals absorb moisture
from the atmosphere, resulting in conductive conditions locally. Unlike what happens
during operation, the solutions that form are oxygenated, and a local corrosive anodic
environment can form at the deposit/blade interface. Such reactions will usually not take
place if the moisture level of the flowing dehumidified environment over the blade
surfaces is kept below 40%. This is the basis for protecting steam path surfaces by flowing
dehumidified air.
The turbine environment during shutdown ultimately controls whether corrosion
damage/failures will occur in the PTZ. Other processes (droplet nucleation, liquid films
and deposits) are unavoidable consequences of thermodynamics and solubility. Shutdown
protection, however, is within the control of the operator.
Corrosion is the most common damage mechanism resulting from deposits. It is discussed
in other parts of Section 3 of this document.
3.2.2 Corrosion
Pitting and localized corrosion are important precursors to more extensive damage from
CF and SCC, although extensive pitting of blades can cause significant loss of stage
efficiency or, in extreme cases, weaken component integrity to the point of failure.
Pitting and localized corrosion are unlikely to originate during turbine operation due to the
absence of oxygen in the liquid films on the turbine surfaces during operation. Rather,
pitting results from corrosive deposits absorbing moist air during turbine shutdown.
During non-protected shutdowns where the blade/disk surfaces are open to the atmosphere,
any deposits, particularly chloride or sulfate, which have formed on steam-path surfaces
during operation can become moist and lead to local, conductive, aqueous environments
that contain ppm levels of oxygen. These local environments initially lead to breakdown of
the blade metal passivity, then to metastable pit formation, and finally to stable pits after
repeated shutdown cycles.15 Each shutdown period is followed by operation where the
dynamic situation of droplet formation, liquid films and deposition occur as described in
Section 3.1. Once a turbine has resumed operation, liquid films can repassivate areas where
passivity was lost during shutdown and metastable pits had formed. However, deposition
continues to occur during operation as described in Section 3.2, and deposits associated
with a loss of passivity that caused a metastable pit during one unprotected shutdown will
lead to further growth of that pit during the next extended unprotected shutdown.
Repetition of this process will eventually lead to a stable pit. Most often, these pits are not
visible, but because they have resulted from an active corrosion mechanism during
shutdown the internal surfaces will be rather irregular. So the different environments which
exist during the repetitive operation and shutdown periods eventually lead to the initiation
and growth of a number of pits on the surface. Analysis needs to be conducted of the
surface geography of the blades and disks in the PTZ rows.
Corrosion Fatigue (CF) and Stress Corrosion Cracking (SCC) of turbine components have
been consistently identified among the main causes of turbine unavailability. Both
phenomena are characterized by two stages: initiation and propagation.
In steam turbines, initiation most frequently occurs at microcracks that emanate from pits
that form when deposits become corrosive during unprotected shutdowns. Cracks can,
however, also initiate on locations of fretting, manufacturing defects, inclusions,
microscopic imperfections, and at areas where specific absorption of species has locally
reduced surface energy. These locations are where deposition will be preferential.
Increased surface roughness acts to increase deposition.
In addition, liquid films of hot NaOH solution can induce severe SCC, even in the absence
of oxygen. At special risk are Stellites and austenitic steels, especially under high internal
13
or external stresses. Low alloy and carbon steel are also at risk at weld joints when no or
inadequate stress-relief heat treatment has been performed.
Propagation of CF and SCC is driven by cyclic or steady stress situations only in regions
where dynamic liquid films are present.
Turbine components may also be attacked by Flow-accelerated Corrosion (FAC) when
liquid films form on turbine components in the presence of two-phase wet steam. Poor
steam purity can cause low pH in such films, and thus trigger or enhance FAC. The use of
Cr-alloyed steels can mitigate and even prevent FAC.16
Solid particle erosion. This is commonly caused by iron oxide particles that scour the
surface of blades, mainly in the initial stages of the HP and IP turbine. The source of such
particles is oxide on superheater and reheater tubes and piping that exfoliates during
transient operation such as startup and shutdown. The growth and exfoliation of these
oxides is not related to steam chemistry.
14
15
number of such compounds are usually proprietary chemicals, and the operators of plants
that use them often do not know what they contain (Section 6.11).
Organics can be a particular problem in industrial plants, where condensate is often
recovered (Section 6.4).
Oxygen has no general relevance in the turbine during operation. In superheat steam,
oxygen content is not relevant for oxide growth.20 In wet steam, due to the large partition
coefficient for oxygen, liquid films have very low oxygen content even when the steam
contains hundreds of g/kg of oxygen. However, steam produced by Boiling Water
Reactors, and steam at any plant under conditions of high oxygen partial pressure in the
condenser (broken vacuum conditions), liquid films can have significant oxygen
concentration that influences corrosion behavior (Sections 6.1 and 6.7).
4.1.2 Conditioning Agents
Solid conditioning agents, such as sodium phosphate and sodium hydroxide, used for
boiler water treatment may cause deposits in the turbine and therefore need to be
considered as potentially corrosive impurities.
Volatile conditioning agents, on the other hand, may separate to some extent into the liquid
phase in the PTZ and provide the possibility for protection. In the superheat part of the
turbine they do not provide any protection.
Ammonia is the most common conditioning agent in the steam/water cycle. Due to its
volatility and relatively weak dissociation, it provides only moderate alkalization in the
liquid films in the turbine to counteract anionic impurities. Care should be taken to avoid
impurities in chemicals added to the cycle, including ammonia, as these could be a source
of chloride.
Reducing Agents. Hydrazine is used in many steam/water cycles where a reducing
environment is required. It decomposes rapidly at temperatures above 400 C and,
therefore, hydrazine is present in steam only in such plants with lower steam temperatures
or when injected directly into the steam. Due to its low volatility, it partitions at
condensation preferentially into the water phase and thus provides better alkalization of the
liquid phase than ammonia.
There are alternative reducing agents, but as these are organic compounds which
decompose, they tend to lead to an increase in CACE in steam.
Amines. Selected amines such as cyclohexylamine, morpholine, ethanolamine and others
offer the possibility of greater partitioning into the liquid phase in the phase transition
zone, as well as stronger alkalization, and thus perhaps better corrosion protection of
turbine components. However, the balance of alkalization between amine and its possible
acidic decomposition products must be considered.
16
4.3 Layup
Conservation of the turbine during shutdown with dry air (relative humidity less than 40%)
is of utmost importance to avoid corrosion during off-line periods, which can further
develop into serious damage during subsequent turbine operation (Sections 3.1.6, 3.2.2 and
6.2).
17
18
Unit
Normal /
Target Values
S/cm
< 0.20
Sodium as Na
g/kg
<2
Silica as SiO2
g/kg
<10
Table 1. Steam purity for condensing utility turbines with superheated steam, applicable for steam
temperature below 600 C.
Unit
Normal /
Target Values
S/cm
< 0.30
Table 2. Steam purity for condensing utility turbines with saturated steam without reheat.
In the event that the steam dries locally, e.g. by expansion in the turbine inlet valve, the
specification for superheated steam should be used.
19
CACE *
g/kg
S/cm
Restrictions
> 20
>2
10 20
12
n 10
n1
20
The instruments for monitoring Na and CACE must be in functional condition at startup.
During shutdown, the main steam pipe and sampling line usually fills with air that will
enter the monitor when the plant resumes operation. Adequate venting and flushing of the
cation resin can reduce the dead time until CACE starts giving good values.21
21
22
If the turbine has been subjected to severe deposition with hygroscopic deposits
(such as NaCl), it is recommended to clean and dry again the turbine beforehand
23
Although industrial turbine inlet steam conditions may differ from those in utility power
plants, the expansion in the LP turbine is similar (Figure 1). Therefore the discussion of the
PTZ in Section 3.1 also applies for these turbines. The potential consequences of operation
with contaminated steam for the turbine as such may be less drastic for industrial turbines
because of the smaller size of the turbine itself, but the direct and indirect cost for
shutdown of a large process dependent on steam from an industrial turbine may be very
high indeed. The concentration of critical contaminants in the steam should therefore, if
possible, be lower than their practical solubility in superheated steam, especially at the area
of any phase transition zone between dry and wet steam.
The position suggested for industrial turbines is to maintain steam chemistry in line with
the limits in Section 5.1. These limits however, especially the limit for CACE, are difficult
and sometimes impossible to meet in many industrial applications, and can be customized
with the options provided in the other parts of Section 6.
There are a few rules that should in any case be applied to every industrial turbine:
In all turbines, trip and throttle valves should be exercised at least once a week to
avoid valve freezing due to deposit buildup. Turbine stage pressures should also be
checked regularly, as deposits on the rotating blades lead to axial shift that may
cause contact between the rotating and stationary parts (Section 3.2.1).
If there are indications of deposit buildup, washing of the turbine (on-line or offline), or other off-line deposit removal options as appropriate (e.g., foam cleaning,
sand blasting) should be considered.
24
The importance of proper layup must be taken into account. Lack of protection
(dehumidified air) during shutdown is the main reason for failure / damage in these
turbines.23
Examples
1. Plants with significant amounts of contaminated return condensate, resulting in high
CACE or other steam chemistry deviations. It is possible to produce steam fulfilling
the limits in Table 1 and Table 2 with a feedwater quality corresponding to softened
water, provided the feedwater is not used for steam attemperation. But this approach is
usually more difficult and costly than with feedwater based on demineralized makeup
water, and it requires a sufficiently low mechanical carryover of boiler water.
2. Plants where the preferred water treatment is based on organic additives as well as
plants where the use of organic additives is due to outsourcing of the management of
water and steam chemistry to chemical vendors, either to save the cost for chemists or
because of a lack of qualified chemists. Thermal decomposition of such organic
additives often results in high steam CACE (Section 6.11).
3. Plants with high and/or persistent in leakage of air, e.g., cycling units. This may result
in high CACE in steam because of high levels of carbon dioxide (Section 6.7).
4. Some industrial plants with a boiler water treatment based on the use of solid
alkalizing agents like Na-Phosphates or NaOH may have difficulty meeting the
sodium limit because of the mechanical carryover of boiler water. This is usually less
critical for plants with pure Na3PO4 treatment where a higher Na limit can be
considered (Section 6.9) than for plants with a treatment based on sodium hydroxide
(Section 3.2.2) or phosphate blends. Hydroxides do not add to the measured CACE
value so a low value does not exclude an excessive content of, e.g., sodium hydroxide
in the steam. This is one of the reasons why sodium should always be measured online
together with CACE. If the limits cannot be met, the following rules mentioned earlier
in this section are of great importance.
5. Industrial turbines are dependent on the operating modes of the industrial process and
are often supplied by varying steam production. If peaking steam production is
accompanied by increased boiler water carryover, it is useful to inspect the turbine
more frequently for deposits. This inspection can be performed, for example, with a
suitable endoscope, without the need to open the turbine.
6. Many industrial turbines are subject to frequent or extended shutdowns. Sections 4.3,
6.1 and 6.2 outline measures for the protection of the turbine during these periods.
7. Frequently, industrial turbines have a common steam supply with other, independently
operating components. If the turbine is shut down, care must be taken to ensure that no
steam can leak from the supply header into the turbine. Such steam leaks create a
moist atmosphere and lead to severe corrosion attack of the turbine. When there are
25
such leaks, normal layup procedures are overwhelmed by the steady supply of
moisture.
8. Industrial plants with copper alloy heat exchangers can have problems with copper
deposition in the same way as discussed in Sections 4.1.1 and 6.13. However, because
few industrial turbines operate above 17 MPa, the harmful effects of copper will not be
in the turbine. Plants may see deposits in the boiler waterwalls, and as already
mentioned in the primary superheater of all plants independent of the pressure.
26
The ability to improve steam purity at direct steam plants may be limited to solid particle
removal, although the development of dry steam scrubbing technologies (adsorbent and
absorbent) is continuing. Direct steam plants may utilize wet steam scrubbing systems if
adequate moisture removal systems are also used and the enthalpy loss of using such
systems is tolerable. Direct steam plants may experience steam purity issues related to
high concentrations of chloride (corrosion) and silica (deposition) among others, while
acidic steam (containing chloride and/or fluoride) can also be of concern and may require
neutralization.
Steam purity at flash plants is largely influenced by the efficiency of the steam separation
system. Steam purity can be further improved with the implementation of steam washing
systems, which usually involve the injection of a small amount of water into the steam and
its later draining to assist in contaminant removal. Flash steam plants may experience
steam purity issues related to high concentrations of chloride (corrosion) and silica
(deposition) among others.
Steam purity in many geothermal power plants is unlikely to meet the steam purity
requirements set out in Sections 5.1 and 6. Geothermal steam turbines are often designed
to handle lower steam purity than that experienced in thermal plants, however the
corrosion and fouling of geothermal steam turbines is still commonplace. Measures to
manage the lower levels of steam purity often include the use of higher grade alloys within
the steam turbine, regular on-line and off-line washing of turbines and regular turbine
outages for inspection and repair.
Due to the lower steam purity experienced in geothermal power plants, the implementation
of the correct turbine shutdown and storage conditions as described in Sections 4.3 and 6.2
is essential for minimizing offline corrosion and damage.
Other features mentioned in Section 6.4 on Industrial Turbines may also be of relevance.
Developing steam purity specifications
As discussed above, steam purity is largely given by the geothermal source, and techniques
to influence it are limited. This results in a wide range of varieties that cannot be fitted into
a simple standard.
A plant steam purity specification will therefore start with the values used for the design of
the turbine. Steam purity monitoring can identify any deviations and in such cases give the
basis for additional corrective measures, as described above and in Section 4.4.
to corrosion and deposits than fossil-fired boilers. Therefore these nuclear steam generating
systems are operated with water purity unmatched in fossil-fired boilers. As a
consequence, the nuclear generated steam has a higher purity and the steam purity
specification can be reduced to a few key parameters.
Superheated steam from nuclear power plants
Steam purity should follow the specifications given in Table 1, monitoring steam chemistry
should follow Section 4.2.
Saturated steam from Boiling Water Reactors (BWR)
In a BWR, steam is generated directly in the nuclear reactor. Cycle chemistry is
characterized by the use of neutral feedwater and reactor water, with no alkalizing agents.
There is no capacity for neutralizing volatile acidic impurities that may condense in the
turbine and can provide a corrosive environment.25 This is aggravated by the oxidizing
environment in the turbine. Without hydrogen chemistry, the oxygen concentration in
steam is up to 10-20 mg/kg, resulting in 100-200 g/kg in the water film at HP turbine inlet
and on the order of 1 g/kg at the beginning of condensation in the LP turbine. With
hydrogen reactor water chemistry, the oxygen levels are lower, but still high enough to
produce an oxidizing environment in the turbine.
Table 4 gives a specification to limit acidic corrosion. Carryover is to be limited in order to
avoid excessive contamination of the turbine by non-volatile activation products like
Co-60. A lower value may be considered depending on feedback from experience of
similar BWR plants.
As the cycle operates under all volatile and neutral water chemistry, the instrumentation for
monitoring steam chemistry can be reduced to a measurement of direct conductivity.
Parameter
Conductivity @ 25 C
Mechanical Carryover *
Unit
S/cm
< 0.10
< 0.1
Table 4. Steam purity for boiling water reactors (N = normal operation limit).
* Percentage of reactor water carried along in the live steam.
Table 5 gives a specification to limit acidic corrosion. A less stringent specification for
cation conductivity may be considered when using amines for water treatment; in such
cases the conditions specified in Section 6.11 should be observed.
Additional requirements should be considered if dissolved solids or compounds of boron
are used as a conditioning agent at any place in the secondary circuit.25 The requirements
regarding Na (Table 5, Sections 4.2 and 6.11) and carryover (Table 5) may be omitted if
only AVT is used for steam generator water treatment.
Parameter
Unit
S/cm
< 0.20
Sodium as Na
g/kg
< 10
< 0.5
Mechanical Carryover *
Table 5. Steam purity for pressurized water reactors with saturated steam (N = normal operation
limit).
* Percentage of steam generator water carried along in the live steam.
29
B. Natural organic matter from the makeup water or cooling water ingress; water
treatment chemicals that do not have alkalizing properties (e.g., many boiler water
dispersants and organic oxygen scavengers). Unlike amines, there is no cation that
can compensate the effect of the acid in the PTZ.
As long as it can be shown that the acidity of the decomposition product in the PTZ is at
least compensated by other products (case A), the acidic decomposition product may be
acceptable, and an additional allowance for CACE can be given. In order to take such an
allowance, plant operators and chemists must know exactly what compounds are added to
the water/steam cycle, and analyze what organic decomposition products are present in the
steam. This is a reason to always include online monitoring of sodium in steam as a
complement to CACE, and why an IC analysis is needed to identify the organic
acids/compounds as well as trace amounts of chlorides and sulfates, as outlined in Section
6.10.
This additional allowance should be such that in no instance will CACE exceed 1 S/cm.
If adequate chemistry information is not available, it is advised to give no extra allowance
in the CACE limits of Section 5.1 for organic decomposition products.
Consideration should also be given to the effect of steam with acidic products on other
equipment of the steam/water cycle, e.g., condenser, feedwater heaters, economizer, etc.18
31
32
IUPAC, Quantities, Units and Symbols in Physical Chemistry, 3rd Edition (RSC Publishing, Cambridge,
2007).
2
IAPWS, Technical Guidance Document: Procedures for the measurement of carryover of boiler water into
steam (2008). Available from http://www.iapws.org.
3
IAPWS, Technical Guidance Document: Instrumentation for monitoring and control of cycle chemistry for
the steam-water circuits of fossil-fired and combined-cycle power plants (2009). Available from
http://www.iapws.org.
4
IAPWS, Technical Guidance Document: Volatile treatments for the steam-water circuits of fossil and
combined cycle/HSRG power plants (2010). Available from http://www.iapws.org.
33
IAPWS, Technical Guidance Document: Phosphate and NaOH treatments for the steam-water circuits of
drum boilers of fossil and combined cycle/HRSG power plants (2011). Available from http://www.iapws.org.
Turbine Steam, Chemistry and Corrosion: Generation of Early Films in Turbines, EPRI Report TR-113090
(1999).
Svoboda, R., and Bodmer, M., Investigations into the Composition of the Water Phase in Steam Turbines,
14th International Conference on the Properties of Water and Steam, Kyoto, Japan, Aug 29 - Sep 3, 2004.
PowerPlant Chemistry 6, 594-601 (2004).
8
Engelhardt, G. R., Macdonald, D. D., and Dooley, R. B., Prediction of Blade and Disc Failures in Low
Pressure Steam Turbines, PowerPlant Chemistry 9, 454-462 (2007).
9
Dooley, R. B., Rieger, N. F. and Bakhtar, F., Studies of Electrostatic Charge Effects Relating to Power
Output from Steam Turbines, PowerPlant Chemistry 7, 69-80 (2005).
10
Jonas, O., and Dooley, R. B., Turbine Steam, Chemistry, and Corrosion, EPRI, TR-108184 (1999).
11
Harvey, A. H., and Bellows, J. C., Evaluation and Correlation of Steam Solubility Data for Salts and
Minerals of Interest in the Power Industry, NIST Technical Note 1387 (US Government Printing Office,
Washington, 1997).
12
Palmer, D. A., Simonson, J. M., and Jensen, J. P., Partitioning of electrolytes in steam and their solubilities
in steam, Chapter 12 of Aqueous Systems at Elevated Temperatures and Pressures: Physical Chemistry in
Water, Steam and Hydrothermal Solutions, D. A. Palmer, R. Fernndez-Prini, and A. H. Harvey, Eds.
(Elsevier, Amsterdam, 2004), ISBN 0-12-544461-3.
13
Bellows, J. C., Mass Transfer and Deposition of Impurities in Steam Turbines, PowerPlant Chemistry 10,
118-122 (2008).
14
15
Engelhardt, G., Macdonald, D., Zhang, Y., and Dooley, B., Deterministic Prediction of Corrosion Damage
in Low Pressure Steam Turbines, 14th International Conference on the Properties of Water and Steam, Kyoto,
Japan, Aug 29 - Sep 3, 2004.
16
Ducreux, J., Theoretical and Experimental Investigation of the Effect of Chemical Composition of Steels
on their Erosion-Corrosion Resistance, Paper 19 presented to the Specialists Meeting on Corrosion-Erosion
of Steels in High Temperature Water and Wet Steam, Les Renardires, France, May 1982.
17
Gruszkiewicz, M., and Bursik, A., Degassed Conductivity Comments on an Interesting and Reasonable
Plant Cycle Chemistry Monitoring Technique, Part 1: Degassing of Low-Molecular-Weight Organic Acids in
Technical Degassed Cation Conductivity Monitors. Power Plant Chemistry 6(3), (2004). Part 2: Degassing
of Carbon Dioxide in Technical Degassed Cation Conductivity Monitors and Temperature Conversion of the
Cation Conductivity Measured at Nearly 100 C to 25 C. Power Plant Chemistry 6(5), 279 (2004).
18
Svoboda, R., Hehs, H., Gabrielli, F., Seipp, H. G., Leidich, F. U., and Roberts, B., Organic Impurities and
Conditioning Agents in the Steam / Water cycle: A Power Plant Manufacturer's Point of View, International
EPRI / PPChem Conference on Interaction of Organics and Organic Cycle Treatment Chemicals with Water,
Steam, and Materials. Stuttgart, Germany, Oct. 4-6, 2005. PowerPlant Chemistry 8, 502-509 (2006).
19
Jonas, O., New Continuous In-line Method for Monitoring Solid Particles and Results of Field Testing, in
S.R. Murphy editor Solid Particle Erosion of Steam Turbine Components: March 1989 Workshop, New
Orleans.
20
Wright, I. G., and Dooley, R. B., A Review of the Oxidation Behavior of Structural Alloys in Steam,
International Materials Reviews 55, 129 (2010).
21
Rziha, M., and Wuhrmann, P., Cation Conductivity Monitoring during Startup, PowerPlant Chemistry 9,
644-648 (2007).
22
Clark, P. J., Effects of Steam Sample Degassing on CCGT Station Startup Profile, PowerPlant Chemistry
12, 246-251 (2010).
34
23
Cycle Chemistry Guidelines for Shutdown, Layup, and Startup of Combined Cycle Units with Heat
Recovery Steam Generators, EPRI Report TR-1010437 (2006).
24
Jonas, O., Determination of Steam Purity Limits for Industrial Turbines, 49th International Water
Conference (1988).
25
Svoboda, R., and Haertel, K., Steam Turbine Chemistry in Light Water Reactor Plants, 15th International
Conference on the Properties of Water and Steam, Berlin / DE, Sep 8-11, 2008; PowerPlant Chemistry 10,
524-529 (2008).
26
IAPWS Certified Research Need 21 (ICRN-21): Thermophysical Properties Associated with Ultrasupercritical Coal-fired Steam Generators. Available from http://www.iapws.org.
27
Cobble, J. W., and Lin, S. W., Chemistry of Steam Cycle Solutions Properties, Chapter 8 of: The ASME
Handbook on Water Technology for Thermal Power Systems (American Society of Mechanical Engineers,
New York, 1989). ISBN 0-7918-0300-7.
28
Svoboda, R., and Bursik, A., Carbon Dioxide and Feedwater Chemistry, PowerPlant Chemistry 7, 472-480
(2005).
29
Svoboda, R., The Effect of Carbon Dioxide and Organics in a Steam Turbine, Second International EPRI /
PPChem Conference on Interaction of Organics and Organic Cycle Treatment Chemicals with Water, Steam,
and Materials. Lucerne, Switzerland, Nov 4-6, 2008. PowerPlant Chemistry 11, 20-27 (2009).
30
Styrikovich, M. A., and Martynova, O. I., Contamination of the Steam in Boiling Reactors from Solution
of Water Impurities, Soviet Atomic Energy 15, 917-921 (1963). ("Ray diagram")
31
Dooley, B., and Shields, K., Alleviation of Copper Problems in Fossil Plants, 14th International
Conference on the Properties of Water and Steam, Kyoto, Japan, Aug 29 - Sep 3, 2004. PowerPlant
Chemistry 6, 497-506 (2004).
32
Howell, F.W., and McConomy, T.A., Maintaining Turbine Capability through Boiler Water Purification,
American Power Conference, 1966, Volume XXVIII, pp. 808-817.
33
Vasilenko, G. V., Zenkevich, Yu. V., and Mazurova, O. K., Features of Fossil Plant Chemistry with
Aluminum Alloy Heat Exchangers, in Water Treatment, Chemistry and Monitoring at Steam Generation
Plants, Vol. 6. (Energya, Moscow, USSR, 1978), pp. 28-31.
34
Mazurova, O. K., Study and Development of Water Chemistry for Large Power Generation Units with
Aluminum-Based Equipment, Ph.D. Thesis. NPO TsKTI, Leningrad, USSR, 1975.
35
IAPWS Certified Research Need 26 (ICRN-26): Behavior of Aluminum in the Steam Water Cycle of
Power Plants. Available from http://www.iapws.org.
35
Figure 1.
Mollier diagram with
three typical turbine
cycles (symbolic
presentation):
A reheat turbine in fossil
fired plant
B backpressure turbine
C reheat turbine in a
nuclear LWR plant
Figure 2.
Solubility limits of SiO2
at various steam
conditions; evaluation of
literature data11,14
Figure 3
Solubility limits of NaCl
at various steam
conditions; evaluation of
literature data11,14
36
No
Yes
(Sections 5.25.5)
Section 6.1
Section 6.2
Backpressure Turbines
Section 6.3
Section 6.4
Section 6.5
Section 6.6
Section 6.7
Section 6.8
Section 6.9
Section 6.10
Section 6.11
Section 6.12
Section 6.13
Figure 4. IAPWS Roadmap to Develop Steam Purity Limits from the Base Table 1 to Specific
Configurations. If a specific case fits into more than one of the listed features, then the
customizations may be combined accordingly.
37