PREPRINT-ICPWS XV

Berlin, September 8-11, 2008

Design Factors and Water Chemistry Practices - Supercritical Power Cycles

Frank Gabrielli
Alstom Windsor, USA, frank.gabrielli@power.alstom.com
and
Horst Schwevers
Alstom Mannheim, Germany, horst.schwevers@power.alstom.com

The paper provides an overview of current supercritical plants with emphasis on boiler design
characteristics, materials of construction for both boilers and turbines and water chemistry requirements.
The paper also discusses material requirements for the ultra-supercritical pressure cycle with pressures and
temperatures approaching 375 bars and 760C. In this respect, it highlights water chemistry and material
issues/requirements that still need to be researched and evaluated.







Introduction

Optimal economy demands high operational
flexibility from power plants, which in turn,
requires that the plants are suitable for a variable
load program and two-shift operation (i.e.
cycling operation). In order to satisfy these
requirements, excellent dynamic behavior and
high load gradients are absolutely essential.
Current supercritical designs have greater
operational flexibility and are better suited for
cycling duty than comparably sized drum units.
However, the requirement for daily cycling
and/or two- shift operation can create
undesirable thermal stresses in the steam turbine
and boiler pressure parts components. These
concerns can be minimized by adopting sliding
pressure operation that significantly minimize
temperature differences in the boiler and steam
turbine systems. The emphasis of designing
more flexible units as well as extending
component life has led to the wide use of sliding
pressure operation.

Basic Design Considerations

Furnace walls are formed by finned or fusion
welded tubes that form a continuous water-
cooled envelope. The biggest concern with any
sliding pressure, supercritical design is created
by the requirement for once-through operation
and designing for sufficiently high mass velocity
that ensures cooling of the furnace tubes.
Drum units maintain the proper mass flows by
the use of either natural or forced circulation.
These boilers are designed to generate steam in
the furnace walls under nucleate boiling
conditions. Nucleate boiling is characterized by
formation and release of steam bubbles at the
surface-liquid interface with the water continues
wetting the inner surface of the tube. The heat
transfer coefficients in the nucleate boiling
regime are high and a temperature gradient
between the metal tube and the fluid inside the
tube is relatively small.
In a once-through boiler, waterwall mass flow
changes in direct proportion to steam flow. In
the supercritical pressure region, the fluid inside
the tubes is heated and the heat is directly
converted into a higher temperature. In the
subcritical once-through pressure region the
process of heat transfer is more complicated and
the process involves a change in phase from
liquid to steam as well as superheating. In most
practical situations, a fluid at a temperature
below its boiling point at the system pressure
enters a furnace tube in which it is heated so that
progressive vaporization and slight superheating
occurs. The process of heat transfer during
vaporization depends on many variables. As the
quality of the steam-liquid mixture increases,
various two-phase flow patterns are encountered.

1

The designers must be concerned with two
critical conditions: Departure from Nucleate
Boiling (DNB) and Dryout (DO). DNB and DO
are characterized by formation of a flow of steam
which covers the inner surface of a tube, a sharp
decrease in heat transfer coefficient, and a
consequent high metal temperature rise. DNB is
of major concern at operating pressures of 2900
psig (204 bar) and higher since, at these
pressures, it is possible for DNB to occur even in
sub-cooled and low quality regions of the
furnace where heat fluxes are relatively high.
While DNB may also occur at lower pressures,
of greater concern at these pressures is DO
which is unavoidable as long as a boiler operates
in once-through mode.
The requirement for once-through operation
brings about a second design challenge; namely,
avoiding potentially damaging stresses resulting
from temperature differences at the furnace wall
outlet. A drum unit always operates with
saturation temperature in the waterwalls and all
circuits are at the same fluid temperature. With a
once- through design, the steam outlet of the
furnace walls is slightly superheated. Therefore,
tube circuits can be at different temperatures due
to the variation in heat absorption patterns
around the furnace perimeter. These temperature
differences must be maintained within acceptable
limits.
Design strategies to deal with the above
concerns are available and are described below.

Spiral Wall Design

The spiral wall design as it stands today has
over thirty years of experience behind it and can
be applied to all unit sizes, pressures, and fuels.
The basic concept of the spiral wall is to increase
the mass flow per tube by reducing the number
of tubes required to envelop the furnace wall
without increasing the spacing between the
tubes. Figure 1 illustrates this concept.




Figure 1. Spiral Wall Design




2




Figure 2. Evaporator Wall Design



Figure 2 shows a comparison between the
inclined tube arrangement and the vertical tube
arrangement. The spiral furnace wall system
employs smooth bore tubes which require high
mass velocity to provide acceptable tube cooling.
The high mass velocity produces high film
conductance that ensures low metal temperatures
and thus economical selection of tube materials.
Fewer and longer tubes combined with higher
mass flow rate, however, produce a higher
pressure drop in the furnace walls.
For a given furnace size and fuel, the expected
heat flux rate determines the mass velocity rate
required to ensure the cooling of the furnace wall
tubes. With a spiral wall design, the number and
size of the tubes are selected to provide sufficient
cooling over the entire load range. Additionally,
by spiraling around the furnace, every tube is
part of all four walls, which means that the
difference in length between the furnace tubes is
minimized and that the heat pickup by individual
tubes is approximately the same. This makes the
spiral wall system less sensitive to changes in the
heat absorption profile in the furnace.
Practical design considerations require a
vertical waterwall configuration in the upper
furnace region. This transition to a vertical wall
is accomplished in a zone where heat fluxes are
relatively low and the requirements on tube
cooling are not as high as in the lower furnace
zone. The transition requires the use of an
intermediate header or bifurcated/trifurcated
fittings.
Due to the fact that the furnace wall tubes are
at an angle, the tubes are not self-supporting.
The supporting load must be transmitted to the
vertical tubes forming the upper section of the
furnace enclosure.

Vertical Wall Rifled Tubing

As an alternative to the spiral wall designs,
Alstom Power has developed a design that uses
conventional vertical tube walls for ease of
construction and maintenance. The design is a
derivative of the Combined Circulation

unit
which we have continually improved since its
introduction in 1961. Rifled tubing is used in the
furnace walls.
A vertical wall configuration typically
employs either 1-1/4 (31.8mm) or 1-1/8
(28.6mm) O.D. internally rifled tubes (Figure 3).
3




Figure 3. Rifled Tube

Rifled tubing offers significant advantages
over smooth tubing in the evaporation range of
sub-critical pressure boiler operation. The use
of rifled tubing permits much lower mass flows
with the same margin of protection against DNB
and overheating. Extensive testing at the Alstom
Power Plant Laboratories has characterized the
heat transfer and flow behavior of rifled tubing
for vertical tube furnace applications.
Rifling promotes turbulence and aids in
wetting the inside tube surface, consequently,
increasing the nucleate boiling quality for a
given heat flux, mass velocity, and pressure.
Similar to the spiral-wound design, the waterwall
panels can be formed by either fin or fusion
welded tubes. Typical average mass velocity per
tube is much smaller than for the spiral
arrangement and still retain more than adequate
margin of safety due to the combined effect of a
smaller tube diameter and rifling.

All once-through supercritical units must be
designed to minimize temperature differences in
the furnace walls. Waterwall outlet temperature
deviations are minimized in the same manner as
on Combined Circulation

designs. This is
accomplished by installing individual tube
orifices that distribute flow in relation to the heat
absorbed by each circuit. Detailed waterwall
analysis based on operating experience and
design practices for Combined Circulation units
show that satisfactory temperature differentials
throughout the entire operating load range can be
achieved with sliding pressure operation. The
temperature difference between the maximum
and minimum value is well within acceptable
range. In addition, there are orifices installed in
a supply sphere (figure 4) to insure that the
prescribed amount of flow is distributed to each
wall.


4




Figure 4. Furnace Waterside Arrangement




Steam Components

Two principal arrangements of heating
surfaces are utilized in Alstom for reheat steam
generators. These are the pendant panel surface
(two-pass) and the horizontal surface (tower)
designs, both of which are used in sub-critical
and supercritical applications. While the basic
concepts of surface arrangements are similar,
there are differences in the location of various
sections in the furnace. The decision to use a
pendant panel design versus a horizontal design
is not dependent on the cycle choice (i.e. sub-
critical vs. supercritical). Each of these
configurations has its advantages and allows for
customer preference as a factor in the final
arrangement of the heating surfaces.

Start-up Systems

General Design Considerations

Todays supercritical power plants are
designed to follow a rigorous load program that
often includes two shift or cycling operations. To
effectively accommodate this operating
requirement, a steam generator must be capable
of sliding pressure operation in the whole
system. This means that during low load and
start-up, the steam generators are operated in a
sub-critical pressure range. Therefore, to
facilitate a satisfactory boiler service, a low load
start-up system is provided. Selection of a
minimum once-through flow/load depends on
such factors as a mode of operation, circuit
stability, and tube materials.
For boilers that are primarily base loaded, the
once-through minimum load should be selected
as high as possible. This results in the lowest
pressure drop in the waterwalls at a full-load
condition. Steam generators that are required to
cycle must be designed for a lower once-through
minimum load so that once-through flow
operation is extended to the lowest load
practical. Commercial experience with a
minimum once-through flow down to 35% to
40% load has proven to be successful. Lower
once-through loads are also feasible. The start -
up system includes a water separator located
between the waterwalls and the primary
superheater, a water storage tank and a drain
water discharge system with heat recovery
capabilities. The water separator consists of one
or more vertical vessels with tangential inlets
(Figure 5).

5



Figure 5. Steam-water separator system and water storage tank


Steam outlets are located in the upper part and
the drain is discharged through the lower part.
The water separator is in wet condition when it
operates in flow recirculation mode and it is
dry when the flow is once-through.
The drain discharge systems with heat
recovery capabilities can be of two types,
indirect heat recovery and direct heat recovery
There are also two types of direct heat
recovery systems that are available. The first one
is a system with a low load recirculation pump;
the second one is a system that includes a drain
return line via a heat exchanger into the
deaerator/feedwater storage tank.
The suitability of each system depends on the
economic evaluation associated with operational
requirements of a steam generator.

Materials and State-of-the-art Steam
Parameters

Except for the waterwalls, where tubing made
of low Cr alloy is used instead of carbon steel,
materials applied in supercritical boiler designs
are similar to materials selected for the drum
type steam generators. The creep rupture strength
and oxidation limit often establish the
temperature limits of a material. For a given
temperature, the creep rupture strength decreases
over time. As the steam parameters increase,
available design margin of many conventional
alloys decreases and, at some temperature level,
their application becomes impractical. The use of
alloys for critical pressure part components such
as waterwalls and finishing superheat/reheat
sections are briefly discussed.

Materials for Water walls

Furnace tubes are subject to the highest heat
flux in the furnace. Typical tubing alloys applied
in the commercial designs are: 1.25 Cr-0.5Mo
(T-12) material, 2.25 Cr 1.0 Mo (T22)
material and a European developed material
15Mo3. These alloys have excellent mechanical
properties suitable for easy fabrication of the
waterwall panels. Design limit of T12 was
studied for a cycle with the superheater outlet
steam conditions up to 4060 psig (280 bar) and
1112F (600 C). For non-corrosive coals and
based on the furnace outlet gas temperature of
2280F (1250C), T12 can be applied in the
waterwalls of tower designs up to the waterwall
outlet temperature of about 880F (470C). T12
is used for lower temperatures in panel designs.
For higher steam conditions and higher water
wall outlet temperatures respectively, different
materials are required. For example, T22 has
slightly higher creep rupture strength and higher
oxidation limit and is frequently used in place of
T12. Its application, however, doesnt enable any
significant increase in cycle parameters. In recent
years, new ferritic alloys became commercially
available that could be applied to water wall
construction. They offer a substantial
improvement in the creep strength and can be
used instead of conventional alloys or enable
higher steam parameters cycle. These materials
6

are 2.25Cr-1.6W-V (T23) alloy (ASME code
approved) developed by Sumitomo Metal
Industries and a 7CrMoVTiB1010 (T24) alloy
developed by Vallourec & Mannesmann Tubes.

Materials for Superheater and Reheater Tubes

When selecting superheater and reheater tube
materials, the creep strength of the selected
alloys must be high enough to provide adequate
margin of safety in the operating pressure and
temperature range. In addition to the requirement
for high strength, the materials corrosion
resistance, both on the flue gas side and on the
steam side, must be considered. Oxides will
always form on the inside and outside surface of
a tube. On some older boiler designs, exfoliating
metal-oxide scale from the internal surfaces of
superheater and reheater tubes, headers, and
piping have been a principal source of solid
particle erosion in steam turbine and valves. The
erosion most frequently occurred in the
intermediate pressure stages and seldom in the
high pressure stages of steam turbines and
valves. The exfoliated oxides are mostly ferritic
types. Low chrome ferritic alloys are
predominant materials throughout the reheater
system and are more prone to exfoliation than
austenitic alloys. Alstom conservative design
practice generally limits application of these
ferritic alloys to relatively low temperatures.
In the past ten years new higher Cr ferritic
containing 9-12% Cr alloys became
commercially available. Ferritic materials allow
for more economical design and have the
advantage of avoiding the problems of dissimilar
metal welds and the large coefficient of
expansion of austenitic steels that are typically
used for higher temperature tubes. These high
chrome ferritic alloys are continuously being
improved for high strength and higher resistance
to oxidation. The addition of Tungsten (W) and
other carbide and nitride forming elements have
led to considerable improvements in the high
temperature strength of the 9-12Cr steels.
However, even for these higher strength alloys
Alstom design practice is to limit their
application to tube outside surface temperature
less than 1200F (650C). For higher
temperatures, austenitic alloys are used.
A new generation of ferritic materials is being
developed which will give enhanced temperature
capabilities relative to those now available. Very
high operating steam temperatures, considered
for higher efficiency cycles, will require the
application of materials with greater creep
strength and greater corrosion resistance than the
best boiler materials in use today. The most
attractive alternative appears to be nickel-base
alloys for the very highest temperature
components. The creep strength is sufficient to
allow operation with steam temperatures of close
to 1300F (705C).

Materials for Turbine Casing and Blades

The HP turbine for live steam temperatures up
to 1100F (594C) is state of the art. For higher
temperatures the design remains the same, only
the materials for valve casings and valve
internals, the diffuser for steam feeding from the
inlet valve to the inlet spiral and the inner casing
itself in the area of increase temperatures are
replaced. Traditionally the Alstom rotor is a
welded construction. The thermally heavily
loaded rotor disk will be adapted by inserting of
a disk of 10 % chromium steel. For the first
turbine blade level an austenitic, for the
subsequent level a martensitic chromium steel is
used. Same applies for the IP turbine, only the
first blade rows are made from nickel base alloy.
The LP turbine final blades suffer from higher
centrifugal forces. Titanium material enables to
realize longer blades with slender and
aerodynamically favorable profiles. So they
allow with the same vacuum bigger steam
turbines with compact dimension. For titanium
final blades there are numerous references in
J apan.

Ultra-Supercritical Cycle

The fundamental need for improved cycle
efficiency capable of variable pressure operation
will require increase in steam temperatures and
pressures. Available materials make cycles with
steam conditions of 4350 psig/1110F/1150F
(300 bar/600C/620C) feasible in todays
market. A number of material development
programs in the US and Europe will enable
primary steam temperatures higher than 1112F
(600C) in not so distant future. For example,
Ni-based alloys are being developed and tested
for higher steam conditions. The European
research project Thermie is aiming at the
development of a cycle with steam conditions at
5440 psig/1290F/1330F (375
bar/700C/720C). The boiler water walls will
need to be constructed of tubes made of higher-
strength, corrosion resistant martensitic steels.
The high-pressure outlet headers, piping, and the
final stage of the superheater tubes will need to
7

be fabricated of Ni-based alloys. Predicted plant
efficiency is approximately 50% based on lower
heating value.

Cycle Corrosion

The utility boiler-turbine cycle is subject to
two basic types of corrosion damage. One type
of corrosion is the general attack on ferritic
materials during periods of adverse feedwater
conditions such as high oxygen concentration in
combination with dissolved contaminants, low
pH, etc. This corrosion may take place
throughout the system. The second type of
corrosion is caused by acid or alkaline
contamination of the boiler water in the presence
of deposited products, and occurs during system
operation.
The effects of oxygen corrosion are two-fold.
First, the resultant pitting can completely
penetrate tube walls. Failures of this type have
predominantly occurred in economizers during
operation, and the superheater and reheater
sections of the boiler under idle conditions.
However, all carbon steel components of the
cycle are potentially susceptible to this type of
failure. Second, the metallic corrosion products
or oxides resulting from oxygen corrosion will
be transported throughout the cycle by the
working fluid which can then foul heat transfer
surfaces and flow sensitive components such as
orifices, turbine passages, etc.
Deviations from recommended chemistry
limits that result in either depressed or elevated
pH values, promote failures of boiler tubing.
These types of attack are accelerated by the
presence of internal metal oxide deposits that
permit soluble contaminants to concentrate
during the process of steam generation or
nucleate boiling. Supercritical units that do not
operate on a sliding pressure mode are generally
not susceptible to this corrosion mechanism
since high contaminant concentrations are not
produced in a single- phase fluid. Also the
presence of condensate polishers in the
feedwater system prevents large amounts of
soluble contaminants from entering the boiler.
Although there are many variations from a
descriptive basis, the majority of these types of
failures can be classified into one of the
following two categories:
1. Caustic corrosion This type of damage is
normally characterized by irregular wastage of
the tube metal beneath a porous deposit. It
progresses to failure when the tube wall thins to
a point where stress rupture occurs locally. In
this process, the microstructure of the metal does
not change and the tubing retains its ductility.
2. Hydrogen damage This type of corrosion
damage usually occurs beneath a relatively dense
deposit. Although some wastage occurs, the tube
normally fails by thick-edge fracture before the
wall thickness is reduced to the point where
stress rupture would occur. Hydrogen, produced
in the corrosion reaction, diffuses through the
underlying metal, producing decarburization and
intergranular microfissuring of the structure.
Brittle fracture occurs along the partially
separated boundaries, and in many cases, an
entire section is blown out from the affected
tube.
Ductile attack is more probable when the
boiler water contains highly soluble alkaline
chemicals such as sodium hydroxide. Hydrogen
damage, on the other hand, is more apt to occur
when a low pH boiler-water environment is
produced as a result of condenser leakage (if
bypasses or leaks through the polisher) or some
other type of system contamination. It is
recognized that the successful operation of a
utility once-through boiler unit with respect to
water technology is coupled to the proper
operation of the condensate demineralizer
system.

Water Treatment Practices

The main objectives of water chemistry
control are to insure the long-term integrity of
the materials of construction and the successful
operation of the boiler-turbine power cycle. The
particular types of chemical treatment may vary
depending on many factors such as the variety of
materials, operating conditions, system design,
etc.
Chemistry control in once-through steam
generating units is based on the following
features:

a. No phase separating devices (i.e. steam drum)
in the system
b. Feedwater, boiler water, and steam are the
same fluid stream
c. Sliding pressure operation includes fluid
conditions typical of both supercritical and sub-
critical operation.

The above design considerations require that
the concentrations of feedwater contaminants be
kept to a minimum and be within allowable
turbine steam purity limits (as specified by the
steam turbine supplier) as the solubility of
8

contaminants increases with higher steam
parameters. Corrosion products transported to
the boiler (or superheater/reheater/turbine) from
the condensate and feedwater system must be
kept at low enough concentrations to minimize
fouling of tube and turbine surfaces, and thus the
potential for damage and/or efficiency losses.
For once-through systems, feedwater
conditioning to minimize general corrosion and
the production of iron oxide can be accomplished
with either all-volatile treatment (AVT) or
oxygenated treatment (OT). Due to the greater
concern for copper transport at supercritical
pressures and its impact on turbine performance,
feedwater systems in these once-through units
consist primarily of ferritic alloys and do not
contain copper alloys downstream of the
condensate polishers.
Controlling feedwater contaminants to a
minimum is critical in once-through units, as
there is no mechanism for their removal once in
the feedwater (downstream of the condensate
polishing system) nor can their aggressive
behavior be arrested by the typical feedwater
chemical treatments (OT or AVT). Contaminant
ingress (from condenser inleakage, makeup
water, etc.) is generally controlled by a
condensate polishing system.
The most frequent contributor to boiler
waterside corrosion, fouling, and failures has
been the accumulation of metal oxide deposits.
These deposits form principally on heat transfer
surfaces but can also foul control orifices that
can then cause overheating of water wall tubes
A reduction in the amount of debris and metal
oxide deposition within the boiler can be
successfully accomplished throughout its life
cycle by:
a. Good storage and on-site erection conditions.
b. Minimum metal oxide concentrations in the
boiler feedwater during startup operations as
well as at load conditions.
c. Adherence to operational water chemistry
guidelines.
d. Adherence to optimum lay-up procedures that
prevent or reduce standby corrosion.
e. Periodic chemical cleanings.
Materials of construction most commonly
used in the condensate and feedwater systems of
once-through utility cycles are ferritic alloys,
stainless steels, and titanium. Copper alloys are
not used in feedwater heaters since copper oxides
can dissolve in the supercritical fluid resulting in
turbine fouling. Carbon and stainless steel tubes
are therefore utilized in feedwater heaters and
stainless steels and titanium are used for
condenser tubes.

Water Treatment Regimes
The Alstom once-through cycle chemistry
guidelines are presented in the appendix (all
listed pH refer to a sample temperature of 25C).
More detailed discussion of the specific
chemistry regimes follows.

AVT (All Volatile Treatment)

AVT is defined as the exclusive use of volatile
conditioning agents. Volatile chemicals
evaporate from the water into the steam in a
gaseous form. When steam condenses, the
chemicals dissolve into the water. They do not
form a solid phase and thus they do not form a
scale or deposit on heat transfer surfaces.
Common volatile conditioning agents are
ammonia, amines, and hydrazine (or hydrazine
substitutes).
With AVT, feedwater pH ranges from 8.8 to
9.8. Low-level AVT has a pH between 8.8-9.3
(especially in plants with copper alloys), and
high level AVT has a pH between 9.2-9.8.
Even though high pH AVT provides better
corrosion protection of steel, it has also its
disadvantages: questions of waste water
treatment, chemicals consumption, exclusion of
ion exchange resin to run in H
+
form.
AVT (R) is defined as AVT that employs a
reducing agent such as hydrazine or other
oxygen scavengers. This results in a low (highly
negative) ECP (electrochemical potential). Thus
the highest possible oxidation state in the oxide
layer is magnetite. It has the disadvantage to
form thicker and more porous magnetite layers
resulting in a higher iron content in the water.
Subsequently ripples can be formed.
It is beneficial in plants with copper heat
exchangers in the feedwater train because it
reduces copper corrosion and therefore the
release of copper into the feedwater. In once-
through systems, the cycle does not however
include copper or its alloys.
AVT (R) also favors Flow Assisted Corrosion
(FAC) in the high pressure feedwater system if it
contains carbon steel alloys therefore, it is not
used as a water treatment regime. The use of
hydrazine for wet lay-up is not relevant for
operating conditions and therefore possible.
Environmental aspects on the use of hydrazine,
however, have to be considered.

9

AVT(O) excludes the use of an oxidizing agent
and therefore, the ECP will be substantially
higher than with AVT(R).
AVT(O) favors the formation of hematite
layers on top of the magnetite, which are less
soluble and hence more stable than the magnetite
layers of AVT(R). As a result, the oxide layer is
thinner and denser and gives more protective
margin against FAC and minimizes orifice
fouling.

OT (Oxygenated Treatment)

OT will provide a high ECP that provides the
formation of hematite layers, which are less
soluble and hence more stable than the magnetite
layers of AVT(R) and the mixed magnetite /
hematite layers of AVT(O). As a result, the level
of iron oxide in the feedwater is much lower. It
gives excellent protective margin against FAC
and minimizes orifice fouling.
As an additional bonus, it has already been
successfully used with very low-level AVT, i.e.
feedwater pH 8.0-8.5. The related small
ammonia concentrations permit a very long life
of H
+
mixed-beds, and ease wastewater
questions.
Of course, OT can also be applied with higher
pH AVT.

OT is not without problems. Oxygen, when
coupled with anions, will be corrosive. OT
therefore requires a strict control of feedwater
impurities (> condensate polishers!)

Conclusions

Large capacity, supercritical units will
continue to play a major role in fulfilling power
generation needs in the global marketplace. The
fundamental need for improved cycle efficiency
capable of variable pressure operation will
require increase in steam temperatures and
pressures, aiming at the development of a cycle
with steam conditions at 5440
psig/1290F/1330F (375 bar/700C/720C). The
boiler waterwalls will need to be constructed of
tubes made of higher-strength, corrosion
resistant martensitic steels. The high-pressure
outlet headers, piping, and the final stage of the
superheater tubes will need to be fabricated of
Ni-based alloys. Turbine components will
include similar alloys as well as titanium in the
LP section. The new applications of these alloys
will in turn require an evaluation of water and
steam chemistry conditions. Cycle chemistry
guidelines would be updated accordingly.
A research need that readily comes to mind is
the behavior or volatility of the various oxides at
these higher temperatures and pressures. It has
also become evident through limited use of these
alloys that development of new chemical
cleaning procedures or solvent mixtures will be
required to effectively remove the oxide scales or
deposits should the need arise.








10


References [7] Deposit and Water Chemistry Studies
with Rifled Tubing, F. Gabrielli, N.
Mohn, B. Teigen, TIS #7530

[8] Komet 650 Coal fired Power Stations
with Steam Temperatures up to 650 C
Findings from a Successful Ten-year
Field to Examine Materials for Boiler
Tubes, Pipes, Turbine and Valves.
Helmut Meyer, Dieter Erdmann, Peter
Moser, Sabine Polenz, VGB PowerTech
3/2008
[1] VGB-D (1988-97) Availability of
thermal power plants

[2] KEMA-NL (1997) Comparison of
subcritical and supercritical units.

[3] The Supercritical Steam Power Plant:
Operational Success and Technological
Advancement, Edward S. Sadlon,
Guenter Scheffknect.

[9] Highly efficient Steam Turbine
Technology for Coal-fired Power
Plants, VGB Symposium Steam
Turbines and Steam Turbine Operation.
A. Tremmel, D. Hartmann, June 2004,
Regensburg, Germany

[4] Analysis and Summary of Rifled Tube
Heat Transfer Date, Mark Palkes, J. H.
Chiu
State-of-the-Art Large
Capacity Sliding Pressure Supercritical
Steam Generators, Mark Palkes,
Edward S. Sadlon, A Salem

[10] EPRI 8th International Cycle Chemistry
Conference. Calgary, Canada. 20-22
J une 2006
[5] NERC-US (1989) Boiler tube failure
trends [11] EPPSA, FDBR and VGB PowerTech
Guidelines for Feedwater, Boiler Water
and Steam for Power Plants/Industrial
Plants, VGB-R450Le, Second Edition
2004

[6] State-of-The-Art Sliding Pressure
Supercritical Steam Generators, Mark
Palkes, John Banas, Gerhard
Weissinger, and Werner Kessel




11

Appendix


STANDARD SPECIFICATIONS FOR ONCE-THROUGH UTILITY BOILER
SYSTEMS (Water Chemistry Requirements for Normal Operation)

1. Demineralized Water (at Demineralizer Water Plant Outlet)
Parameter Unit N A1* A2 S** An

Specific conductivity S/cm <0.10 0.1-0.2 - 0.2 c
at storage tank outlet *** S/cm <1 1 - - c
Silica as SiO
2
ppb <10 10 - 20 - 20 c
Sodium +Potassium as Na+K ppb <5 - - - m
Iron as Fe ppb <20 - - - m
TOC ppb <300 - - - m
Oxygen - satur.

A1* - indicates that there is a problem
- actions shall be taken to bring values to normal
- operation may be continued as long as feedwater/steam specifications are
not jeopardized
S** do not put this water into the demineralized water storage tank
*** conductivity as measured at demineralized water storage tank outlet,
including carbon dioxide

2. Condensate (at Hotwell Outlet)

Parameter Unit N A1 A2 S An

Specific conductivity S/cm 2.5 - 11 --- --- --- m
Conductivity after cation exch. S/cm <0.20 0.2 - 0.5 >0.5 >1 c
pH-value --- 9.0 - 9.6* --- --- --- m
Iron as Fe ppb <20 --- --- --- m
* for oxygenated treatment, values in accordance with those in Table 4
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3. Feedwater (AVT Treatment - measurements at economizer inlet)
Parameter Unit N A1 A2 S An

Specific conductivity S/cm 4.0-11 --- --- --- c
Conductivity after cation exch. S/cm <0.20 0.2 - 0.5 >0.5 >1 c
pH-value --- 9.2 - 9.6 <9.2
>9.6
>10 7 * c
Sodium +Potassium as Na+K ppb <5 5 - 10 10 - 20 >20 m or
c
Silica as SiO
2
ppb <20 20 ** --- --- m
Iron as Fe ppb <20 --- --- --- m
Hydrazine ppb *** m

Oxygen ppb <10 50 **** --- --- c
* if dosing is limited during system refilling, ammonia will be below normal. In such a case,
pH 5.5 is tolerated
** time permitted above A1 see Main steam
*** hydrazine or equivalent should not be used if O
2
<10 ppb
**** no cumulative time limit for exceeding A1



4. Feedwater (Oxygenated Treatment instead of AVT)

Parameter Unit N A1 A2 S An

Specific conductivity S/cm 2.5 - 7.0 --- --- --- c
Conductivity after cation exch. S/cm <0.20 0.2 - 0.5 * >0.5 * >1 c
pH-value - 8.5 - 9.0 --- --- --- c
Sodium +Potassium as Na+K ppb <5 5 - 10 10-20 >20 m or
c

Oxygen ** ppb 50 -150 --- --- --- c
* discontinue oxygen injection
** target for oxygen injection
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5. Main Steam and Reheat Steam (at OTSG Outlet)

Parameter Unit N A1 A2 S An

Specific conductivity S/cm 2.5 - 7.0 --- --- --- m
Conductivity after cation exch. S/cm <0.20 0.2 - 0.5 >0.5 >1 c
pH-value - 9.0 - 9.6* --- --- --- m
Sodium +Potassium as Na+K ppb <5 5 -10 10 - 20 >20 m or
c
Silica as SiO
2
ppb <20 20 ** --- --- c

Iron as Fe ppb <20 --- --- --- m
* see Section 4 if on oxygen treatment
** time permitted above 20 ppb with an Alstom steam turbine: [hours]*[ppb] <10
5
. If this time has
expired, turbine pressure and efficiency must be measured. If turbine capacity/efficiency has
degraded, the turbine should be cleaned.

6. General Remarks

All conductivities are referred to 25C. Possible contributions from carbon dioxide may be
excluded.

Operation is desirable at the lowest achievable impurity levels, with the shortest and least
frequent excursions.

The specification is related to the following conditions:
There are no copper alloys in the system
Conditioning is done with ammonia and oxygen injection.

Note: This is a general specification, valid for the plant type mentioned only. The criteria will
be reviewed for a specific application and at commissioning.

Except where defined otherwise in the footnote of a table, the following definitions apply:




N Normal Value. Values are consistent with long-term system reliability. A safety margin has
been provided to avoid concentration of contaminants at surfaces.
A1 Action Level 1. There is a potential for the accumulation of contaminants and corrosion.
Return to normal values within 1 week. Maximum exposure is 336 cumulative hours per
year, excluding start-up conditions.
A2 Action Level 2. The accumulation of impurities and corrosion will occur. Return to normal
levels within 24 hours. Maximum exposure is 48 cumulative hours per year, excluding start-
up conditions.
S Immediate Shutdown. Immediate shutdown of the concerned system is required to avoid
damage.



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Once-Through Boiler Cycle - Guidelines for Initial Start-up and Restarts
After Long Outages


1. Flush to waste until suspended solids in the condensate, feedwater and boiler water are
less than 3ppm (a). The feedwater (b) can be pumped through the boiler into the start-up
separator, flash tank (if present), and then to waste.

2. When this limit is achieved, circulate water through boiler, start-up separator, flash tank
and back to condenser. Place condensate demineralizers in service.

3. When total iron concentration drops below 1 ppm, silica is less than 100 ppb, and cation
conductivity is less than 1uS/cm (c), unit firing can commence. Boiler and start-up system operation
should be as per instruction manual.

4. Proceed to normal feedwater control limits (c). These should be obtained before
exceeding one-third unit load.

(a). Permissible value depends on demineralizer performance/constraints.
(b). Feedwater pH >9.
(c). Parameters measured at economizer inlet.


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