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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 and designing for sufficiently high mass velocity


that ensures cooling of the furnace tubes.
Optimal economy demands high operational Drum units maintain the proper mass flows by
flexibility from power plants, which in turn, the use of either natural or forced circulation.
requires that the plants are suitable for a variable These boilers are designed to generate steam in
load program and two-shift operation (i.e. the furnace walls under nucleate boiling
cycling operation). In order to satisfy these conditions. Nucleate boiling is characterized by
requirements, excellent dynamic behavior and formation and release of steam bubbles at the
high load gradients are absolutely essential. surface-liquid interface with the water continues
Current supercritical designs have greater wetting the inner surface of the tube. The heat
operational flexibility and are better suited for transfer coefficients in the nucleate boiling
cycling duty than comparably sized drum units. regime are high and a temperature gradient
However, the requirement for daily cycling between the metal tube and the fluid inside the
and/or two- shift operation can create tube is relatively small.
undesirable thermal stresses in the steam turbine In a once-through boiler, waterwall mass flow
and boiler pressure parts components. These changes in direct proportion to steam flow. In
concerns can be minimized by adopting sliding the supercritical pressure region, the fluid inside
pressure operation that significantly minimize the tubes is heated and the heat is directly
temperature differences in the boiler and steam converted into a higher temperature. In the
turbine systems. The emphasis of designing subcritical once-through pressure region the
more flexible units as well as extending process of heat transfer is more complicated and
component life has led to the wide use of sliding the process involves a change in phase from
pressure operation. liquid to steam as well as superheating. In most
practical situations, a fluid at a temperature
Basic Design Considerations below its boiling point at the system pressure
enters a furnace tube in which it is heated so that
Furnace walls are formed by finned or fusion progressive vaporization and slight superheating
welded tubes that form a continuous water- occurs. The process of heat transfer during
cooled envelope. The biggest concern with any vaporization depends on many variables. As the
sliding pressure, supercritical design is created quality of the steam-liquid mixture increases,
by the requirement for once-through operation various two-phase flow patterns are encountered.

1
The designers must be concerned with two circuits are at the same fluid temperature. With a
critical conditions: Departure from Nucleate once- through design, the steam outlet of the
Boiling (DNB) and Dryout (DO). DNB and DO furnace walls is slightly superheated. Therefore,
are characterized by formation of a flow of steam tube circuits can be at different temperatures due
which covers the inner surface of a tube, a sharp to the variation in heat absorption patterns
decrease in heat transfer coefficient, and a around the furnace perimeter. These temperature
consequent high metal temperature rise. DNB is differences must be maintained within acceptable
of major concern at operating pressures of 2900 limits.
psig (204 bar) and higher since, at these Design strategies to deal with the above
pressures, it is possible for DNB to occur even in concerns are available and are described below.
sub-cooled and low quality regions of the
furnace where heat fluxes are relatively high. Spiral Wall Design
While DNB may also occur at lower pressures,
of greater concern at these pressures is DO The spiral wall design as it stands today has
which is unavoidable as long as a boiler operates over thirty years of experience behind it and can
in once-through mode. be applied to all unit sizes, pressures, and fuels.
The requirement for once-through operation The basic concept of the spiral wall is to increase
brings about a second design challenge; namely, the mass flow per tube by reducing the number
avoiding potentially damaging stresses resulting of tubes required to envelop the furnace wall
from temperature differences at the furnace wall without increasing the spacing between the
outlet. A drum unit always operates with tubes. Figure 1 illustrates this concept.
saturation temperature in the waterwalls and all

Figure 1. Spiral Wall Design

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Figure 2. Evaporator Wall Design

Figure 2 shows a comparison between the furnace region. This transition to a vertical wall
inclined tube arrangement and the vertical tube is accomplished in a zone where heat fluxes are
arrangement. The spiral furnace wall system relatively low and the requirements on tube
employs smooth bore tubes which require high cooling are not as high as in the lower furnace
mass velocity to provide acceptable tube cooling. zone. The transition requires the use of an
The high mass velocity produces high film intermediate header or bifurcated/trifurcated
conductance that ensures low metal temperatures fittings.
and thus economical selection of tube materials. Due to the fact that the furnace wall tubes are
Fewer and longer tubes combined with higher at an angle, the tubes are not self-supporting.
mass flow rate, however, produce a higher The supporting load must be transmitted to the
pressure drop in the furnace walls. vertical tubes forming the upper section of the
For a given furnace size and fuel, the expected furnace enclosure.
heat flux rate determines the mass velocity rate
required to ensure the cooling of the furnace wall Vertical Wall Rifled Tubing
tubes. With a spiral wall design, the number and
size of the tubes are selected to provide sufficient As an alternative to the spiral wall designs,
cooling over the entire load range. Additionally, Alstom Power has developed a design that uses
by spiraling around the furnace, every tube is conventional vertical tube walls for ease of
part of all four walls, which means that the construction and maintenance. The design is a
difference in length between the furnace tubes is derivative of the Combined Circulation unit
minimized and that the heat pickup by individual which we have continually improved since its
tubes is approximately the same. This makes the introduction in 1961. Rifled tubing is used in the
spiral wall system less sensitive to changes in the furnace walls.
heat absorption profile in the furnace. A vertical wall configuration typically
Practical design considerations require a employs either 1-1/4 (31.8mm) or 1-1/8
vertical waterwall configuration in the upper (28.6mm) O.D. internally rifled tubes (Figure 3).

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Figure 3. Rifled Tube

Rifled tubing offers significant advantages


over smooth tubing in the evaporation range of All once-through supercritical units must be
sub-critical pressure boiler operation. The use designed to minimize temperature differences in
of rifled tubing permits much lower mass flows the furnace walls. Waterwall outlet temperature
with the same margin of protection against DNB deviations are minimized in the same manner as
and overheating. Extensive testing at the Alstom on Combined Circulation designs. This is
Power Plant Laboratories has characterized the accomplished by installing individual tube
heat transfer and flow behavior of rifled tubing orifices that distribute flow in relation to the heat
for vertical tube furnace applications. absorbed by each circuit. Detailed waterwall
Rifling promotes turbulence and aids in analysis based on operating experience and
wetting the inside tube surface, consequently, design practices for Combined Circulation units
increasing the nucleate boiling quality for a show that satisfactory temperature differentials
given heat flux, mass velocity, and pressure. throughout the entire operating load range can be
Similar to the spiral-wound design, the waterwall achieved with sliding pressure operation. The
panels can be formed by either fin or fusion temperature difference between the maximum
welded tubes. Typical average mass velocity per and minimum value is well within acceptable
tube is much smaller than for the spiral range. In addition, there are orifices installed in
arrangement and still retain more than adequate a supply sphere (figure 4) to insure that the
margin of safety due to the combined effect of a prescribed amount of flow is distributed to each
smaller tube diameter and rifling. wall.

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Figure 4. Furnace Waterside Arrangement

Steam Components system. This means that during low load and
start-up, the steam generators are operated in a
Two principal arrangements of heating sub-critical pressure range. Therefore, to
surfaces are utilized in Alstom for reheat steam facilitate a satisfactory boiler service, a low load
generators. These are the pendant panel surface start-up system is provided. Selection of a
(two-pass) and the horizontal surface (tower) minimum once-through flow/load depends on
designs, both of which are used in sub-critical such factors as a mode of operation, circuit
and supercritical applications. While the basic stability, and tube materials.
concepts of surface arrangements are similar, For boilers that are primarily base loaded, the
there are differences in the location of various once-through minimum load should be selected
sections in the furnace. The decision to use a as high as possible. This results in the lowest
pendant panel design versus a horizontal design pressure drop in the waterwalls at a full-load
is not dependent on the cycle choice (i.e. sub- condition. Steam generators that are required to
critical vs. supercritical). Each of these cycle must be designed for a lower once-through
configurations has its advantages and allows for minimum load so that once-through flow
customer preference as a factor in the final operation is extended to the lowest load
arrangement of the heating surfaces. practical. Commercial experience with a
minimum once-through flow down to 35% to
Start-up Systems 40% load has proven to be successful. Lower
once-through loads are also feasible. The start -
General Design Considerations up system includes a water separator located
between the waterwalls and the primary
Todays supercritical power plants are superheater, a water storage tank and a drain
designed to follow a rigorous load program that water discharge system with heat recovery
often includes two shift or cycling operations. To capabilities. The water separator consists of one
effectively accommodate this operating or more vertical vessels with tangential inlets
requirement, a steam generator must be capable (Figure 5).
of sliding pressure operation in the whole

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

Steam outlets are located in the upper part and as waterwalls and finishing superheat/reheat
the drain is discharged through the lower part. sections are briefly discussed.
The water separator is in wet condition when it
operates in flow recirculation mode and it is Materials for Water walls
dry when the flow is once-through.
The drain discharge systems with heat Furnace tubes are subject to the highest heat
recovery capabilities can be of two types, flux in the furnace. Typical tubing alloys applied
indirect heat recovery and direct heat recovery in the commercial designs are: 1.25 Cr-0.5Mo
There are also two types of direct heat (T-12) material, 2.25 Cr 1.0 Mo (T22)
recovery systems that are available. The first one material and a European developed material
is a system with a low load recirculation pump; 15Mo3. These alloys have excellent mechanical
the second one is a system that includes a drain properties suitable for easy fabrication of the
return line via a heat exchanger into the waterwall panels. Design limit of T12 was
deaerator/feedwater storage tank. studied for a cycle with the superheater outlet
The suitability of each system depends on the steam conditions up to 4060 psig (280 bar) and
economic evaluation associated with operational 1112F (600 C). For non-corrosive coals and
requirements of a steam generator. based on the furnace outlet gas temperature of
2280F (1250C), T12 can be applied in the
Materials and State-of-the-art Steam waterwalls of tower designs up to the waterwall
Parameters outlet temperature of about 880F (470C). T12
is used for lower temperatures in panel designs.
Except for the waterwalls, where tubing made For higher steam conditions and higher water
of low Cr alloy is used instead of carbon steel, wall outlet temperatures respectively, different
materials applied in supercritical boiler designs materials are required. For example, T22 has
are similar to materials selected for the drum slightly higher creep rupture strength and higher
type steam generators. The creep rupture strength oxidation limit and is frequently used in place of
and oxidation limit often establish the T12. Its application, however, doesnt enable any
temperature limits of a material. For a given significant increase in cycle parameters. In recent
temperature, the creep rupture strength decreases years, new ferritic alloys became commercially
over time. As the steam parameters increase, available that could be applied to water wall
available design margin of many conventional construction. They offer a substantial
alloys decreases and, at some temperature level, improvement in the creep strength and can be
their application becomes impractical. The use of used instead of conventional alloys or enable
alloys for critical pressure part components such higher steam parameters cycle. These materials

6
are 2.25Cr-1.6W-V (T23) alloy (ASME code strength and greater corrosion resistance than the
approved) developed by Sumitomo Metal best boiler materials in use today. The most
Industries and a 7CrMoVTiB1010 (T24) alloy attractive alternative appears to be nickel-base
developed by Vallourec & Mannesmann Tubes. alloys for the very highest temperature
components. The creep strength is sufficient to
Materials for Superheater and Reheater Tubes allow operation with steam temperatures of close
to 1300F (705C).
When selecting superheater and reheater tube
materials, the creep strength of the selected Materials for Turbine Casing and Blades
alloys must be high enough to provide adequate
margin of safety in the operating pressure and The HP turbine for live steam temperatures up
temperature range. In addition to the requirement to 1100F (594C) is state of the art. For higher
for high strength, the materials corrosion temperatures the design remains the same, only
resistance, both on the flue gas side and on the the materials for valve casings and valve
steam side, must be considered. Oxides will internals, the diffuser for steam feeding from the
always form on the inside and outside surface of inlet valve to the inlet spiral and the inner casing
a tube. On some older boiler designs, exfoliating itself in the area of increase temperatures are
metal-oxide scale from the internal surfaces of replaced. Traditionally the Alstom rotor is a
superheater and reheater tubes, headers, and welded construction. The thermally heavily
piping have been a principal source of solid loaded rotor disk will be adapted by inserting of
particle erosion in steam turbine and valves. The a disk of 10 % chromium steel. For the first
erosion most frequently occurred in the turbine blade level an austenitic, for the
intermediate pressure stages and seldom in the subsequent level a martensitic chromium steel is
high pressure stages of steam turbines and used. Same applies for the IP turbine, only the
valves. The exfoliated oxides are mostly ferritic first blade rows are made from nickel base alloy.
types. Low chrome ferritic alloys are The LP turbine final blades suffer from higher
predominant materials throughout the reheater centrifugal forces. Titanium material enables to
system and are more prone to exfoliation than realize longer blades with slender and
austenitic alloys. Alstom conservative design aerodynamically favorable profiles. So they
practice generally limits application of these allow with the same vacuum bigger steam
ferritic alloys to relatively low temperatures. turbines with compact dimension. For titanium
In the past ten years new higher Cr ferritic final blades there are numerous references in
containing 9-12% Cr alloys became Japan.
commercially available. Ferritic materials allow
for more economical design and have the Ultra-Supercritical Cycle
advantage of avoiding the problems of dissimilar
metal welds and the large coefficient of The fundamental need for improved cycle
expansion of austenitic steels that are typically efficiency capable of variable pressure operation
used for higher temperature tubes. These high will require increase in steam temperatures and
chrome ferritic alloys are continuously being pressures. Available materials make cycles with
improved for high strength and higher resistance steam conditions of 4350 psig/1110F/1150F
to oxidation. The addition of Tungsten (W) and (300 bar/600C/620C) feasible in todays
other carbide and nitride forming elements have market. A number of material development
led to considerable improvements in the high programs in the US and Europe will enable
temperature strength of the 9-12Cr steels. primary steam temperatures higher than 1112F
However, even for these higher strength alloys (600C) in not so distant future. For example,
Alstom design practice is to limit their Ni-based alloys are being developed and tested
application to tube outside surface temperature for higher steam conditions. The European
less than 1200F (650C). For higher research project Thermie is aiming at the
temperatures, austenitic alloys are used. development of a cycle with steam conditions at
A new generation of ferritic materials is being 5440 psig/1290F/1330F (375
developed which will give enhanced temperature bar/700C/720C). The boiler water walls will
capabilities relative to those now available. Very need to be constructed of tubes made of higher-
high operating steam temperatures, considered strength, corrosion resistant martensitic steels.
for higher efficiency cycles, will require the The high-pressure outlet headers, piping, and the
application of materials with greater creep final stage of the superheater tubes will need to

7
be fabricated of Ni-based alloys. Predicted plant this process, the microstructure of the metal does
efficiency is approximately 50% based on lower not change and the tubing retains its ductility.
heating value. 2. Hydrogen damage This type of corrosion
damage usually occurs beneath a relatively dense
Cycle Corrosion deposit. Although some wastage occurs, the tube
normally fails by thick-edge fracture before the
The utility boiler-turbine cycle is subject to wall thickness is reduced to the point where
two basic types of corrosion damage. One type stress rupture would occur. Hydrogen, produced
of corrosion is the general attack on ferritic in the corrosion reaction, diffuses through the
materials during periods of adverse feedwater underlying metal, producing decarburization and
conditions such as high oxygen concentration in intergranular microfissuring of the structure.
combination with dissolved contaminants, low Brittle fracture occurs along the partially
pH, etc. This corrosion may take place separated boundaries, and in many cases, an
throughout the system. The second type of entire section is blown out from the affected
corrosion is caused by acid or alkaline tube.
contamination of the boiler water in the presence Ductile attack is more probable when the
of deposited products, and occurs during system boiler water contains highly soluble alkaline
operation. chemicals such as sodium hydroxide. Hydrogen
The effects of oxygen corrosion are two-fold. damage, on the other hand, is more apt to occur
First, the resultant pitting can completely when a low pH boiler-water environment is
penetrate tube walls. Failures of this type have produced as a result of condenser leakage (if
predominantly occurred in economizers during bypasses or leaks through the polisher) or some
operation, and the superheater and reheater other type of system contamination. It is
sections of the boiler under idle conditions. recognized that the successful operation of a
However, all carbon steel components of the utility once-through boiler unit with respect to
cycle are potentially susceptible to this type of water technology is coupled to the proper
failure. Second, the metallic corrosion products operation of the condensate demineralizer
or oxides resulting from oxygen corrosion will system.
be transported throughout the cycle by the
working fluid which can then foul heat transfer Water Treatment Practices
surfaces and flow sensitive components such as
orifices, turbine passages, etc. The main objectives of water chemistry
Deviations from recommended chemistry control are to insure the long-term integrity of
limits that result in either depressed or elevated the materials of construction and the successful
pH values, promote failures of boiler tubing. operation of the boiler-turbine power cycle. The
These types of attack are accelerated by the particular types of chemical treatment may vary
presence of internal metal oxide deposits that depending on many factors such as the variety of
permit soluble contaminants to concentrate materials, operating conditions, system design,
during the process of steam generation or etc.
nucleate boiling. Supercritical units that do not Chemistry control in once-through steam
operate on a sliding pressure mode are generally generating units is based on the following
not susceptible to this corrosion mechanism features:
since high contaminant concentrations are not
produced in a single- phase fluid. Also the a. No phase separating devices (i.e. steam drum)
presence of condensate polishers in the in the system
feedwater system prevents large amounts of b. Feedwater, boiler water, and steam are the
soluble contaminants from entering the boiler. same fluid stream
Although there are many variations from a c. Sliding pressure operation includes fluid
descriptive basis, the majority of these types of conditions typical of both supercritical and sub-
failures can be classified into one of the critical operation.
following two categories:
1. Caustic corrosion This type of damage is The above design considerations require that
normally characterized by irregular wastage of the concentrations of feedwater contaminants be
the tube metal beneath a porous deposit. It kept to a minimum and be within allowable
progresses to failure when the tube wall thins to turbine steam purity limits (as specified by the
a point where stress rupture occurs locally. In steam turbine supplier) as the solubility of

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contaminants increases with higher steam stainless steels and titanium are used for
parameters. Corrosion products transported to condenser tubes.
the boiler (or superheater/reheater/turbine) from
the condensate and feedwater system must be Water Treatment Regimes
kept at low enough concentrations to minimize The Alstom once-through cycle chemistry
fouling of tube and turbine surfaces, and thus the guidelines are presented in the appendix (all
potential for damage and/or efficiency losses. listed pH refer to a sample temperature of 25C).
For once-through systems, feedwater More detailed discussion of the specific
conditioning to minimize general corrosion and chemistry regimes follows.
the production of iron oxide can be accomplished
with either all-volatile treatment (AVT) or AVT (All Volatile Treatment)
oxygenated treatment (OT). Due to the greater
concern for copper transport at supercritical AVT is defined as the exclusive use of volatile
pressures and its impact on turbine performance, conditioning agents. Volatile chemicals
feedwater systems in these once-through units evaporate from the water into the steam in a
consist primarily of ferritic alloys and do not gaseous form. When steam condenses, the
contain copper alloys downstream of the chemicals dissolve into the water. They do not
condensate polishers. form a solid phase and thus they do not form a
Controlling feedwater contaminants to a scale or deposit on heat transfer surfaces.
minimum is critical in once-through units, as Common volatile conditioning agents are
there is no mechanism for their removal once in ammonia, amines, and hydrazine (or hydrazine
the feedwater (downstream of the condensate substitutes).
polishing system) nor can their aggressive With AVT, feedwater pH ranges from 8.8 to
behavior be arrested by the typical feedwater 9.8. Low-level AVT has a pH between 8.8-9.3
chemical treatments (OT or AVT). Contaminant (especially in plants with copper alloys), and
ingress (from condenser inleakage, makeup high level AVT has a pH between 9.2-9.8.
water, etc.) is generally controlled by a Even though high pH AVT provides better
condensate polishing system. corrosion protection of steel, it has also its
The most frequent contributor to boiler disadvantages: questions of waste water
waterside corrosion, fouling, and failures has treatment, chemicals consumption, exclusion of
been the accumulation of metal oxide deposits. ion exchange resin to run in H+ form.
These deposits form principally on heat transfer AVT (R) is defined as AVT that employs a
surfaces but can also foul control orifices that reducing agent such as hydrazine or other
can then cause overheating of water wall tubes oxygen scavengers. This results in a low (highly
A reduction in the amount of debris and metal negative) ECP (electrochemical potential). Thus
oxide deposition within the boiler can be the highest possible oxidation state in the oxide
successfully accomplished throughout its life layer is magnetite. It has the disadvantage to
cycle by: form thicker and more porous magnetite layers
a. Good storage and on-site erection conditions. resulting in a higher iron content in the water.
b. Minimum metal oxide concentrations in the Subsequently ripples can be formed.
boiler feedwater during startup operations as It is beneficial in plants with copper heat
well as at load conditions. exchangers in the feedwater train because it
c. Adherence to operational water chemistry reduces copper corrosion and therefore the
guidelines. release of copper into the feedwater. In once-
d. Adherence to optimum lay-up procedures that through systems, the cycle does not however
prevent or reduce standby corrosion. include copper or its alloys.
e. Periodic chemical cleanings. AVT (R) also favors Flow Assisted Corrosion
Materials of construction most commonly (FAC) in the high pressure feedwater system if it
used in the condensate and feedwater systems of contains carbon steel alloys therefore, it is not
once-through utility cycles are ferritic alloys, used as a water treatment regime. The use of
stainless steels, and titanium. Copper alloys are hydrazine for wet lay-up is not relevant for
not used in feedwater heaters since copper oxides operating conditions and therefore possible.
can dissolve in the supercritical fluid resulting in Environmental aspects on the use of hydrazine,
turbine fouling. Carbon and stainless steel tubes however, have to be considered.
are therefore utilized in feedwater heaters and

9
AVT(O) excludes the use of an oxidizing agent steam chemistry conditions. Cycle chemistry
and therefore, the ECP will be substantially guidelines would be updated accordingly.
higher than with AVT(R). A research need that readily comes to mind is
AVT(O) favors the formation of hematite the behavior or volatility of the various oxides at
layers on top of the magnetite, which are less these higher temperatures and pressures. It has
soluble and hence more stable than the magnetite also become evident through limited use of these
layers of AVT(R). As a result, the oxide layer is alloys that development of new chemical
thinner and denser and gives more protective cleaning procedures or solvent mixtures will be
margin against FAC and minimizes orifice required to effectively remove the oxide scales or
fouling. deposits should the need arise.

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

10
References [7] Deposit and Water Chemistry Studies
with Rifled Tubing, F. Gabrielli, N.
Mohn, B. Teigen, TIS # 7530

[1] VGB-D (1988-97) Availability of [8] Komet 650 Coal fired Power Stations
thermal power plants with Steam Temperatures up to 650 C
Findings from a Successful Ten-year
[2] KEMA-NL (1997) Comparison of Field to Examine Materials for Boiler
subcritical and supercritical units. Tubes, Pipes, Turbine and Valves.
Helmut Meyer, Dieter Erdmann, Peter
[3] The Supercritical Steam Power Plant: Moser, Sabine Polenz, VGB PowerTech
Operational Success and Technological 3/2008
Advancement, Edward S. Sadlon,
Guenter Scheffknect. [9] Highly efficient Steam Turbine
Technology for Coal-fired Power
[4] Analysis and Summary of Rifled Tube Plants, VGB Symposium Steam
Heat Transfer Date, Mark Palkes, J. H. Turbines and Steam Turbine Operation.
Chiu A. Tremmel, D. Hartmann, June 2004,
State-of-the-Art Large Regensburg, Germany
Capacity Sliding Pressure Supercritical
Steam Generators, Mark Palkes, [10] EPRI 8th International Cycle Chemistry
Edward S. Sadlon, A Salem Conference. Calgary, Canada. 20-22
June 2006
[5] NERC-US (1989) Boiler tube failure
trends [11] EPPSA, FDBR and VGB PowerTech
Guidelines for Feedwater, Boiler Water
[6] State-of-The-Art Sliding Pressure and Steam for Power Plants/Industrial
Supercritical Steam Generators, Mark Plants, VGB-R450Le, Second Edition
Palkes, John Banas, Gerhard 2004
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 SiO2 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

12
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 > 10 7* c
> 9.6
Sodium + Potassium as Na+K ppb <5 5 - 10 10 - 20 > 20 m or
c
Silica as SiO2 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 O2 < 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

13
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 SiO2 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] <105. 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.

14
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.

15

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