EPRI Start Up, Lay Up & Shut Down Guidelines For Chemist

Cycling, Startup, Shutdown, and
Layup Fossil Plant Cycle Chemistry

Guidelines for Operators and
Chemists
TR-107754
Final Report, August 1998
EPRI Project Manager

Barry Dooley
EPRI 3412 Hillview Avenue, Palo Alto, California 94304 PO Box 10412, Palo Alto, California 94303 USA
800.313.3774 650.855.2121 askepri@epri.com www.epri.com
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CITATIONS
This report was prepared by
EPRI
3412 Hillview Avenue
Palo Alto, CA 94403
This report describes research sponsored by EPRI. It is a corporate document that
should be cited in the literature in the following manner:
Cycling, Startup, Shutdown, and Layup Fossil Plant Cycle Chemistry Guidelines for Operators
and Chemists, EPRI, Palo Alto, CA, 1998.TR-107754.
iii
REPORT SUMMARY
The purity of water and steam is central to ensuring fossil plant component availability
and reliability. This report will assist utilities in developing cycle chemistry guidelines
for all transient operation and shutdown.
Background
EPRI has published four operating guidelines for phosphate treatment, all-volatile
treatment, oxygenated treatment, and caustic treatment. These guidelines encompass
five drum boiler water treatments and three feedwater choices that can provide the
optimum cycle chemistry for each unit. A similar, consistent approach was needed for
startup, shutdown, and layup. Improper shutdown of a unit can lead to pitting, which
is a precursor to major corrosion fatigue and stress corrosion damage in the turbine. It
can also lead to the development of nonprotective oxides on copper alloys in the
feedwater.
Objective
To provide comprehensive guidelines for cycle chemistry during startup, shutdown,
and layup of fossil plants; to provide optimum procedures for the boiler, superheater,
reheater, turbine, and feedwater heaters.
Approach
EPRI developed an initial skeleton of the guidelines that provided the basis for a series
of working group meetings with members of the EPRI Fossil Plant Cycle Chemistry
Group (FPCCG). Following these meetings, EPRI and five of its cycle chemistry
consultants developed a draft document and circulated it to the 40 members of the
FPCCG for review and comment.
Results
This guideline provides the final link needed for comprehensive coverage of cycle
chemistry in fossil plants. It provides specific procedures and advice during cycling,
shutdown, startup, and layup for each of the boiler and feedwater treatments and
v
covers all major water and steam touched surfaces. The guideline is applicable to drum
boiler units above 600 psi (4.1MPA), once-through subcritical and supercritical boiler
units, units with and without condensate polishers, all-ferrous and mixed metallurgy
feedwater systems, and superheaters, reheaters and turbines.
EPRI Perspective
While most utilities can meet EPRI cycle chemistry guideline limits, a large number of
problem areas have been identified that relate to poor transient (startup/shutdown)
operation and improper layup procedures. Two such important mechanisms are pitting
in unprotected reheaters, which can lead to multiple reheater leaks. and pits on low
pressure turbine blade/disk surfaces in the phase transition zone. A very low
percentage of utilities currently provide shutdown protection to boilers, feedwater
heaters, and turbines. This document will provide the important interfaces between
plant operation, plant shutdown, and transient conditions.
TR-107754
Interest Categories
Fossil steam plant O&M cost reduction
Fossil steam plant performance optimization
Applied science and technology
Keywords
Power plant availability
Water chemistry
Cycling
Startup
Shutdown
Layup
vi
EPRI Licensed Material
ABSTRACT
EPRIs initial interim consensus guidelines, issued in 1986, have recently been replaced
by four guidelines which address four boiler water treatments:
x
Phosphate treatment for drum boiler units,
All-Volatile treatment for drum and once-through units,
Oxygenated treatment for drum and once-through units,
Caustic treatment for drum units,
and three feedwater treatments:

x
All-volatile treatment for all-ferrous metallurgy systems with and without reducing
agents (oxygen scavengers),
All-volatile treatment for mixed metallurgy systems with reducing agents (oxygen
scavengers),
Oxygenated treatment for all-ferrous metallurgy systems.
A recent report provides the guidance for effective and economic selection and
optimization of boiler water and feedwater treatment for each unit.
This current guideline provides the final link needed for comprehensive coverage of
cycle chemistry in fossil plants. It provides specific procedures and advice during
cycling, shutdown, startup and layup for each of the boiler and feedwater treatments.
It covers all the major water and steam touched surfaces.
Sections 2 and 3 include information, which is common to all units and chemistries:
metallurgical, corrosion, design and operating considerations. The definitions used
throughout the guideline are provided in Section 3.
vii
Section 4 provides information on layup and shutdown considerations common to most

units: wet and dry layup, and dehumidification for all the major power plant
components.
Sections 5-8 deal with specific procedures for cycling, shutdown, startup, and layup for
phosphate treatments, all-volatile treatment, oxygenated treatment and caustic
treatment respectively.
viii
ACKNOWLEDGMENTS
The authors of these guidelines:
R. B. Dooley, EPRI
A. Aschoff, EPRI Consultant
M. Ball, EPRI Consultant
A. Bursik, EPRI Consultant
O. Jonas, EPRI Consultant of Jonas Inc.
and
F. Pocock, EPRI Consultant
acknowledge that the two earlier drafts of this guideline were reviewed by the 41
members of the Fossil Plant Cycle Chemistry Group (FPCCG). The authors further
acknowledge the contributions from the following members of the FPCCG:
B. Conlin
D. Goldstrohm
A. Howell
D. E. Hubbard
A. Lindberg
J. Matthews
V. Mrasek
K. J. Shields
W. Urion
ESKOM
Salt River Project
New Century Energies
American Electric Power
Commonwealth Edison
Duke Power
Public Service Company of Oklahoma
Sheppard D. Powell Associates
Connectiv
During the preparation of these guidelines two Target 51 member utilities also
provided extensive documentation on their layup experiences which are
complementary to the procedures in the guidelines:
Iberdrola
Spain
Ecogen Energy Australia
This report was word processed by Lorrain Sargent of Pacific Publications, and all the
figures were drawn by Marilyn Winans of the EPRI Graphics Office.
ix
CONTENTS
1 INTRODUCTION ................................................................................................................. 1-1

1.1 OVERVIEW OF THE EPRI FOSSIL PLANT CYCLE CHEMISTRY PROGRAM .......... 1-1
Volatility of Salts in Steam Cycles ................................................................................... 1-2
Phosphate Chemistry/Hideout/Corrosion ........................................................................ 1-4
Deposition and Chemical Cleaning ................................................................................. 1-6
Steam, Chemistry and Corrosion in the Phase Transition Zone (PTZ)............................ 1-6
1.2 EPRI FOSSIL PLANT GUIDELINES AND MANAGEMENT APPROACHES FOR
CYCLE CHEMISTRY .......................................................................................................... 1-7
1.3 NEED AND DEVELOPMENT FOR CYCLING/SHUTDOWN/STARTUP/LAYUP
GUIDELINES ...................................................................................................................... 1-9
1.4 OBJECTIVES OF THESE GUIDELINES ................................................................... 1-10
1.5 SCOPE OF THESE GUIDELINES............................................................................. 1-11
1.6 REFERENCES .......................................................................................................... 1-11
2 METALLURGICAL, DESIGN, AND OPERATING CONSIDERATIONS.............................. 2-1
2.1 INTRODUCTION.......................................................................................................... 2-1
Impurity Generation, Transport, and Corrosion Effects ................................................... 2-3
Steam Cycle Materials and Their Properties ................................................................... 2-8
Material Properties .......................................................................................................... 2-9
2.2 STEAM CYCLE COMPONENT CORROSION AND DEPOSITS ................................. 2-9
Basics of Material Corrosion ........................................................................................... 2-9
Cycle Component Damage Mechanisms ...................................................................... 2-17
2.3 PREBOILER SYSTEMS - ALL FERROUS VS. MIXED METALLURGY .................... 2-21
All-Ferrous Feedwater Systems(3, 4) ................................................................................ 2-22
Mixed Metallurgy Feedwater Systems (Copper Containing)(3, 4, 22, 28)................................ 2-24
Copper Transport .......................................................................................................... 2-25
2.4 PRIORITIES FOR TRANSIENT OPERATION ........................................................... 2-26
xi
2.5 EFFECTS OF STEAM CYCLE DESIGN AND OPERATION ..................................... 2-29

Drum Boiler vs. Once-through Boiler Units(7-12) ............................................................... 2-30
Sliding Pressure Operation(17,39-42) ................................................................................... 2-30
Boiler Concerns(15-17,25,39,40,43-46) .............................................................................................. 2-30
Turbine(18,42,49,50) ................................................................................................................... 2-33
Turbine Bypass Systems(43,49.50) .......................................................................................... 2-38
Feedwater System Cleanup Loops(14,45,46,52,53,54) ................................................................... 2-39
Condensate Filtering and Polishing(15,45,54,67)........................................................................ 2-41
Air Inleakage and Deaeration(15,45,53-61)................................................................................. 2-41
Condenser Deaeration .................................................................................................. 2-47
2.6 ALTERNATIVE WATER TREATMENT CHEMICALS(3,63,64) ......................................... 2-47
2.7 REFERENCES AND BIBLIOGRAPHY FOR SECTION 2 .......................................... 2-49
3 GENERAL ASPECTS COMMON TO MOST UNITS ........................................................... 3-1
3.1 DEFINITIONS .............................................................................................................. 3-1
Cycling ............................................................................................................................ 3-1
Duration of Shutdown...................................................................................................... 3-1
Forced Shutdown ............................................................................................................ 3-2
System Failure but no Equipment Failure ................................................................... 3-3
Major Equipment Failure ............................................................................................. 3-3
3.2 USE OF POLISHERS AND CONDENSATE FILTRATION .......................................... 3-3
Condensate Polishing and/or Filtration(1b) ........................................................................ 3-3
Makeup Water Treatment................................................................................................ 3-3
3.3 MONITORING IMPORTANCE AND REQUIREMENTS ............................................... 3-4
Sampling and Monitoring ................................................................................................ 3-4
Sampling Problems ......................................................................................................... 3-4
3.4 MAJOR CHEMICAL TRANSIENT................................................................................ 3-5
Chemical Transients and Equipment Failures................................................................. 3-6
3.5 MINIMIZATION OF AIR IN-LEAKAGE ......................................................................... 3-7
3.6 CORRECTIVE ACTIONS............................................................................................. 3-8
3.7 HOW TO USE THE PRESENT EPRI GUIDELINES FOR CYCLING
OPERATION....................................................................................................................... 3-8
Drum Units ...................................................................................................................... 3-9
Once-Through Units...................................................................................................... 3-10
xii
3.8 OPERATING PROCEDURES.................................................................................... 3-10

3.9 ENVIRONMENTAL CONSIDERATIONS ................................................................... 3-10
3.10 REFERENCES ........................................................................................................ 3-11
4 SHUTDOWN AND LAYUP CONSIDERATIONS COMMON TO MOST UNITS................... 4-1
4.1 INTRODUCTION.......................................................................................................... 4-1
4.2 LAYUP PRACTICES.................................................................................................... 4-2
Short-term vs. Longterm Layup....................................................................................... 4-3
4.3 WET LAYUP (12-15) ......................................................................................................... 4-8
4.4 DRY LAYUP USING DEHUMIDIFIED AIR................................................................... 4-9
4.5 FEEDWATER HEATERS, CONDENSER, REHEATER AND TURBINE.................... 4-14
Turbine.......................................................................................................................... 4-15
Feedwater Side of Condensers and Feedwater Heaters .............................................. 4-16
Shell Side Feedwater Heaters....................................................................................... 4-16
Superheater .................................................................................................................. 4-16
Deaerator and Storage Tank......................................................................................... 4-17
4.6 LAYUP MONITORING ............................................................................................... 4-17
4.7 ENVIRONMENTAL CONSIDERATIONS ................................................................... 4-17
4.8 ROAD MAP FOR SHUTDOWN AND LAYUP ............................................................ 4-18
4.9 REFERENCES .......................................................................................................... 4-22
5 PHOSPHATE TREATED DRUM UNITS.............................................................................. 5-1
5.1 INTRODUCTION.......................................................................................................... 5-1
5.2 CURRENT NORMAL OPERATING GUIDELINES....................................................... 5-2
5.3 STARTUP PROCEDURES ........................................................................................ 5-10
Road Map ..................................................................................................................... 5-11
5.4 CYCLING AND PEAKING UNITS .............................................................................. 5-12
5.5 SHUTDOWN PROCEDURES.................................................................................... 5-12
Road Map ..................................................................................................................... 5-14
5.6 MIXED METALLURGY SYSTEMS ............................................................................ 5-16
5.7 CORRECTIVE ACTIONS........................................................................................... 5-17
5.8 LAYUP ....................................................................................................................... 5-17
5.9 REFERENCES .......................................................................................................... 5-18
6 ALL-VOLATILE TREATMENT ............................................................................................ 6-1
xiii
6.1 INTRODUCTION.......................................................................................................... 6-1

6.2 ONCE-THROUGH UNITS............................................................................................ 6-2
Current Guidelines .......................................................................................................... 6-2
Startup ............................................................................................................................ 6-2
Shutdown ........................................................................................................................ 6-7
Cycling and Peaking ..................................................................................................... 6-10
Layup ............................................................................................................................ 6-11
6.3 DRUM BOILERS WITH ALL-FERROUS FEEDWATER HEATING SYSTEMS.......... 6-11
Current Guidelines ........................................................................................................ 6-11
Startup .......................................................................................................................... 6-18
Shutdown ...................................................................................................................... 6-22
Layup ............................................................................................................................ 6-26
6.4 DRUM UNITS WITH MIXED METALLURGY FEEDWATER HEATING SYSTEMS ... 6-27
Current Guidelines ........................................................................................................ 6-28
Startup .......................................................................................................................... 6-28
Shutdown ...................................................................................................................... 6-32
Layup ............................................................................................................................ 6-36
6.5 REFERENCES .......................................................................................................... 6-36
7 OXYGENATED TREATMENT ............................................................................................. 7-1
7.1 INTRODUCTION.......................................................................................................... 7-1
7.2 ALL-FERROUS CYCLES WITH ONCE-THROUGH BOILERS.................................... 7-2
Current Normal Operating Guidelines ............................................................................. 7-2
Startup Procedures ......................................................................................................... 7-4
Shutdown Procedures..................................................................................................... 7-7
Short-Term Shutdown. ................................................................................................ 7-8
Longterm Shutdown. ................................................................................................... 7-9
Emergency Shutdown. .............................................................................................. 7-10
Shutdown as a Result of a Serious Chemistry Excursion.......................................... 7-10
Cycling and Peaking Operation(3-7) ................................................................................. 7-10
Layup Practices............................................................................................................. 7-11
7.3 ALL-FERROUS CYCLES WITH DRUM BOILERS..................................................... 7-12
xiv
Current Normal Operating Guidelines ........................................................................... 7-12

Startup Procedures ....................................................................................................... 7-14
Shutdown Procedures................................................................................................... 7-19
Short-Term Shutdown. .............................................................................................. 7-19
Longterm Shutdown. ................................................................................................. 7-20
Emergency Shutdown. .............................................................................................. 7-21
Shutdown as a Result of a Serious Chemistry Excursion.......................................... 7-22
Cycling and Peaking Operation..................................................................................... 7-23
Layup Practices............................................................................................................. 7-23
7.4 REFERENCES .......................................................................................................... 7-24
8 CAUSTIC TREATMENT FOR DRUM BOILERS ................................................................. 8-1
8.1 INTRODUCTION.......................................................................................................... 8-1
8.2 ALL-FERROUS FEEDWATER HEATING SYSTEMS.................................................. 8-2
Current Guidance Document........................................................................................... 8-2
Startup ............................................................................................................................ 8-2
Shutdown ........................................................................................................................ 8-5
Cycling and Peaking ....................................................................................................... 8-5
Layup .............................................................................................................................. 8-7
8.3 MIXED METALLURGY FEEDWATER HEATING SYSTEMS ...................................... 8-7
Current Guidelines .......................................................................................................... 8-9
Startup ............................................................................................................................ 8-9
Shutdown ...................................................................................................................... 8-11
Layup ............................................................................................................................ 8-12
8.4 REFERENCES .......................................................................................................... 8-12
xv
LIST OF FIGURES
Figure 1-1 Partitioning Constants KD for Common Boiler Water Salts, Acids and Bases
Represented by Mathematical Functions of the Reciprocal of Temperature in
Kelvin up to the Critical Temperature of Water, Tc.......................................................... 1-4
Figure 2-1 Three supports for reliable cycling operation ........................................................ 2-2
Figure 2-2 Typical water chemistry and corrosion effects of layup, startup and cycling
for a drum boiler cycle ..................................................................................................... 2-4
Figure 2-3 Sources of contaminants enhanced by cycling operation and examples of
engineering solutions. ..................................................................................................... 2-5
Figure 2-4 Mollier diagram for a fossil cycle........................................................................... 2-6
Figure 2-5 Potential - pH diagram for carbon steel in 300 C water (19).................................. 2-11
Figure 2-6 Corrosion of mild steel and solubility of magnetite at 300C, showing
corrosion rate laws(15,20.21) ................................................................................................ 2-12
Figure 2-7 Potential - pH diagram for copper in ammonia solutions at 25C (22) .................... 2-13
Figure 2-8 Average copper release as a function of pH....................................................... 2-14
Figure 2-9 Effect of pH on steady state release rates for 90Cu/10Ni and 70Cu/30Ni
exposed to ammonia solutions containing 8-21 g/kg oxygen, flowing at ~1ft/s
(0.3m/s) and at a temperature of 35 - 38C(22) .............................................................. 2-15
Figure 2-10 Corrosion fatigue diagram for NiCrMoV LP turbine disk and rotor steel18 ........ 2-16
Figure 2-11 Stress corrosion of NiCrMoV disk steel vs. yield strength for "good" water
and steam(18) .................................................................................................................. 2-17
Figure 2-12 The effect of pH on iron and copper concentration at the economizer inlet.
Source: D. Frey, Mechanics of Corrosion Product Formation and Transport(14) ............ 2-22
Figure 2-13 Calculated and measured HP rotor temperatures - startup .............................. 2-34
Figure 2-14 Turbine fatigue index vs. temperature change and time (51) ............................... 2-37
Figure 2-15 Turbine valves for partial arc and full arc admission ......................................... 2-37
Figure 2-16 Rotor thermal stress as a function of time with sliding pressure. Initial
throttle to metal temperature difference = +50F, throttle temperature ramp =
200F/h, loading rate = 2% per minute.......................................................................... 2-37
Figure 2-17 Turbine bypass system..................................................................................... 2-39
Figure 2-18 Condensate/feedwater cleanup loops(46) ........................................................... 2-40
Figure 2-19 Expected dissolved oxygen at the deaerator outlet vs. load for tray and
spray deaerators ........................................................................................................... 2-43
Figure 2-20 Condenser deaerating capacity with and without retrofitted devices(62) ............. 2-44
xvii
Figure 2-21 Cycle iron concentration during a cold startup for two layup practices(62) .......... 2-45
Figure 2-22 Effect of air-saturated makeup water on condensate oxygen level (59) ............... 2-46
Figure 3-1 Metals Concentrations in Feedwater During Startup Operations(9,10) ..................... 3-5
Figure 4-1 Nitrogen blanketing of a drum boiler showing the nitrogen connections(12). .......... 4-7
Figure 4-2 Corrosion Rate of Steel Relative to Humidity of Air ............................................ 4-10
Figure 4-3 Rotary Desiccant Dehumidifier(17) ........................................................................ 4-11
Figure 4-4 Block Diagram of Dehumidifier Steam/Feed Cycle(18) .......................................... 4-12
Figure 4-5 Steamside Dehumidification Flow(19) ................................................................... 4-13
Figure 4-6 Turbine dry layup using dehumidified air(23) ......................................................... 4-16
Figure 4-7 Dry layup of 107 MW turbine showing measured values of temperature
(F/C) and air humidity ................................................................................................. 4-16
Figure 4-8 Road Map to Develop Shutdown and Layup Guidelines Common to Most
Units.............................................................................................................................. 4-18
Figure 5-1 Older Forms of Phosphate Treatment .................................................................. 5-3
Figure 5-2 Schematic of Operating Ranges of Boiler Water on Equilibrium Phosphate
Treatment (EPT), Congruent Phosphate Treatment (CPT) and Phosphate
Treatment (PT)(1). The CPT is shown to its maximum Na:PO4 molar ratio of 2.8; the
normal operating range is below the Na:PO4 molar ratio of 2.6....................................... 5-4
Figure 5-3 Cycle Chemistry Diagram for a Drum Unit on Equilibrium Phosphate
Treatment (Plants With Reheat)Core Parameters Marked. ......................................... 5-5
Figure 5-4 Equilibrium Phosphate Treatment: Boiler Water Sodium vs. Operating
Pressure (Plants With Reheat)........................................................................................ 5-6
Figure 5-5 Equilibrium Phosphate Treatment: Boiler Water Chloride vs. Operating
Figure 5-6 Equilibrium Phosphate Treatment: Boiler Water Sulfate vs. Operating
Figure 5-7 Equilibrium Phosphate Treatment: Boiler Water Silica vs. Operating
Figure 5-8 Road Map for Startup of PT or EPT Units .......................................................... 5-10
Figure 5-9 Road Map for Shutdown of PT or EPT Units (This should be used in
conjunction with Figure 4-8.) ......................................................................................... 5-13
Figure 6-1 Cycle Chemistry Diagram for a Once-Through Unit on All-Volatile Treatment...... 6-3
Figure 6-2 Startup of Once-through Units with All-Ferrous Feedwater Heaters ..................... 6-5
Figure 6-3 AVT - Shutdown of Once-Through Units with All-Ferrous Feedwater Heaters ...... 6-8
Figure 6-4 Cycle Chemistry Diagram for a Drum Unit on All-Volatile Treatment (Plants
with Reheat) .................................................................................................................. 6-12
Figure 6-5 All Volatile Treatment: Drum Boiler Water Sodium vs. Operating Pressure
(Plants With Reheat) ..................................................................................................... 6-13
Figure 6-6 All-Volatile Treatment: Drum Boiler Water Chloride vs. Operating Pressure
xviii
Figure 6-7 All-Volatile Treatment: Drum Boiler Water Sulfate vs. Operating Pressure
Figure 6-8 All-Volatile Treatment: Drum Boiler Water Silica vs. Operating Pressure
Figure 6-9 All-Volatile Treatment: Drum Boiler Water Cation Conductivity vs. Operating
Pressure (Plants With Reheat)...................................................................................... 6-17
Figure 6-10 AVT - Startup of Drum Boilers with All-Ferrous Feedwater Heaters ................. 6-20
Figure 6-11 AVT - Shutdown of Units with Drum Boilers with All-Ferrous and Mixed
Metallurgy Feedwater Heaters ...................................................................................... 6-23
Figure 6-12 AVT - Startup of Drum Boilers with Mixed Metallurgy Feedwater Heaters........ 6-30
Figure 7-1 Cycle Chemistry Diagram of Once-Through Units on Oxygenated Treatment
(core parameters only) .................................................................................................... 7-3
Figure 7-2 Road map for the startup of once-through boilers operated with OT.................... 7-5
Figure 7-3 Shutdown and Operation Guidance for OT Chemistry for Short-Term
Shutdowns ...................................................................................................................... 7-8
Figure 7-4 Shutdown and Operation Guidance for OT Chemistry for Long-Term
Shutdowns. Note *: Dependent on wet or dry storage and utilization of nitrogen
blanketing (See Section 4) .............................................................................................. 7-9
Figure 7-5 Cycle Chemistry Diagram of Drum Units on Oxygenated Treatment (OT).......... 7-13
Figure 7-6 Road map for the startup of drum boilers operated with OT............................... 7-16
Figure 7-7 Operation and Shutdown Guidance for OT Chemistry for Short-term
Shutdowns (Drum Boiler Unit) ....................................................................................... 7-20
Figure 7-8 Operation and Shutdown for OT Chemistry for Longterm Shutdowns (Drum
Boiler Unit) .................................................................................................................... 7-21
Figure 8-1 Cycle Chemistry Diagram for Drum Type Coal-Fired Boiler on Sodium
Hydroxide Treatment (Plants with Reheat)...................................................................... 8-3
Figure 8-2 CT - Startup of Drum Boilers with All-Ferrous Feedwater Heaters........................ 8-6
Figure 8-3 CT - Shutdown of Drum Boilers with All-Ferrous and Mixed Metallurgy
Feedwater Heaters.......................................................................................................... 8-7
Figure 8-4 CT - Startup of Drum Boilers with Mixed Fe-Cu Metallurgy Feedwater
Heaters ......................................................................................................................... 8-11
xix
LIST OF TABLES
Table 1-1 Core Monitoring Parameters (Minimum level of instruments for all
plants/units)..................................................................................................................... 1-8
Table 2-1 Transient Effects and Their Amelioration.............................................................. 2-7
Table 2-2 Boiler Tube Damage Mechanisms Influenced by Cycle Chemistry (Adapted
from reference 27) (Discussion of each mechanism can be found in Reference 25) .... 2-18
Table 2-3 Turbine Deposits & Damage Mechanisms Influenced by Cycle Chemistry
(Adapted from reference 27) (Discussion of each mechanism can be found in
Reference 65) ............................................................................................................... 2-19
Table 2-4 Condensate/Feedwater Cycle Damage Mechanisms Influenced by Startup
Cycle Chemistry (Adapted from reference 27) .............................................................. 2-20
Table 2-5 Generation of Feedwater Corrosion Products by Corrosion and FlowAccelerated Corrosion, and the Major Unit Transport and Deposition Problem
Areas for All-Ferrous Systems....................................................................................... 2-23
Table 2-6 Generation of Feedwater Corrosion Products by Corrosion and FlowAccelerated Corrosion, and the Major Unit Transport and Deposition Problem
Areas for Mixed Metallurgy Systems ............................................................................. 2-25
Table 2-7 List of Concerns for Cycling Units (CH indicates the items affected by water
and steam chemistry) .................................................................................................... 2-28
Table 4-1 Shutdown and Layup Alternatives Showing Advantages and Disadvantages
for Each Alternative......................................................................................................... 4-4
xxi
1
INTRODUCTION
These guidelines cover water and steam chemistry control during transient operation
including cycling and peaking, cold and warm startups, shutdown, and layup. They
do not cover mechanical and thermal restraints imposed by equipment manufacturers
and cycle design. However, these restraints, which often have the highest priority, are
considered in the chemical guidelines and limits.
1.1 OVERVIEW OF THE EPRI FOSSIL PLANT CYCLE CHEMISTRY

PROGRAM
The Electric Power Research Institute (EPRI) Fossil Plant Cycle Chemistry Program has
the following goals:
x
To eliminate boiler tube failures related to cycle chemistry
To eliminate turbine chemical problems (low-pressure blade and disk cracks, and
serious deposits throughout the turbine)
To develop optimized feedwater treatment:
elimination of serious flow-accelerated corrosion (FAC)
low iron and copper transport (<2 ppb at the economizer inlet)
To eliminate the need for boiler chemical cleaning
To provide simple, reliable cycle chemistry instrumentation and control:
core levels of instrumentation for all plants
expert advisor
direct on-line, in-situ instruments
To shorten the startup period by:
1-1

Introduction
optimization of shutdown, lay-up and startup chemistry
the elimination of unnecessary chemical holds in the startup sequence
To develop operational guidelines with action levels for all units, and
To provide the optimum managerial approach in support of cycle chemistry
The program was initiated with the development of the Interim Consensus Guidelines
(ICG) in 1986(1).
(2, 3)
The ICG was followed by a detailed monitoring program at four US fossil plants .
Information was also collected at many international plants(4). The information that was
developed from these efforts led to the identification of four areas where the
understanding was deficient in the derivation of the ICG chemistry limits:
Volatility of salts and how impurities partition between boiler water and steam
Phosphate chemistry/hideout/corrosion
Deposition around the cycle
Steam chemistry and corrosion in the phase transition zone (PTZ)
EPRI projects have been initiated in response to these areas of deficiency. Brief
information on these studies is included below together with information from other
studies with particular emphasis for developing these current guidelines on
cycling/shutdown/startup and layup.
Volatility of Salts in Steam Cycles

Historically the ray diagram has provided a rough estimate for determining
vaporous carryover from the boiler water. But it was confirmed from plant
monitoring(2, 3) that chloride and sulfate concentrations can be as much as two orders of
magnitude higher in the steam than shown in the ray diagram.
To develop a more thorough understanding of the volatility of salts in steam cycles, the
EPRI research in this area began by investigating the partitioning of ammonium
chloride (NH4Cl) in laboratory-scale experiments from 120C (248F) to 350C (662F)(5).
This research revealed that while the dominant chloride species for NH4Cl solutions in
both high and low temperature liquid were NH4+ and Cl-, the species transported to the
equilibrated vapor were predominantly HCl and NH3. An approximately similar
picture has emerged from the continued research on the partitioning from sulfate
solutions in the presence of sodium and ammonium cations, although the hydrolysis
1-2

Introduction
reactions of sulfate ion complicate the speciation. The significant species in solution at
low temperature (condensate, blowdown) under AVT conditions are ammonium ions,
ammonia, and hydroxide ions, with impurities of sulfur being present in the form of
sulfate ions. At boiler operating conditions, equilibrium thermodynamics dictate that
ammonia predominates over ammonium ion, whereas bisulfate and sulfate ions are at
much lower, but similar, concentrations. In the high temperature steam phase at
equilibrium with this solution, again ammonia predominates over HCl. At lower, but
comparable, concentration levels are ammonium chloride, sodium hydroxide, sulfuric
acid, sodium bisulfate and ammonium bisulfate, depending on the relative levels of
these impurities in the boiler water. These preliminary calculations predict further
rearrangement of the relative concentrations of the predominant molecules as the steam
cools, with a much larger range in values. Clearly the situation is more complex with
the addition of more potentially-volatile species, particularly those which undergo
additional reactions in the liquid phase, and this complex chemistry goes far beyond
that which can be predicted from the ray diagram. The partitioning constants for
typical fossil plant salts, acids and bases are shown in Figure 1-1, where the
partitioning constant, KD, can be defined for a simple 1:1 electrolyte as the ratio of the
concentration of the neutral molecule in the vapor phase to the activities of the
component ions in the liquid phase.
1-3

Introduction
TC
Temperature (C)
300
200
150
20
10
NH3
Log KD
HCI
H2SO4
NH4Cl
NH4HSO4
NaCl
-10
NaOH
Na2SO4
-20
NaHSO4
1.4
1.6
1.8
2.0
2.2
2.4
2.6
1 x 103
K
Figure 1-1 Partitioning Constants KD for Common Boiler Water Salts, Acids and
Bases Represented by Mathematical Functions of the Reciprocal of Temperature
in Kelvin up to the Critical Temperature of Water, Tc.
Phosphate Chemistry/Hideout/Corrosion
Up to the mid 1990s many utilities continued to experience phosphate hideout and
boiler water pH instability when following the information on congruent phosphate
treatment (CPT) in the ICG(1). Hideout and hideout return occurred on every startup
and shutdown respectively. This essentially made chemical control for cycling units
1-4

Introduction
very difficult. Also, an increasing number of utilities experienced serious internal

corrosion (attributed to acid phosphate corrosion) of the boiler waterwalls and
subsequent boiler tube failures when using this phosphate chemistry (6, 7). The sodium
iron phosphate compound, maricite, has been found to be a magnetite-phosphate
reaction product associated with cases of serious corrosion, and a distinguishing
difference from caustic gouging.
An EPRI project(8, 9) was initiated to answer questions related to boiler tube corrosion
and phosphate hide-out that have occurred in some boilers operating under CPT and
to assist in modifying the ICG. This work generally extended the results of the 1964-68
ASME Test Program(10). The results are in general agreement with the literature
published on this subject. Specifically, no evidence of major corrosion attack was found
using phosphate based boiler water treatment under conditions of:
x
Saturation pressure of 2800 psig (19.3 Mpa) and heat flux up to 200,000 BTU/hr ft2
(630kW/m2)
Departure from nucleate boiling (DNB) 12 hours in duration
Phosphate concentration to 10 ppm
Sodium to phosphate molar ratios ranging from 1.84.0
Magnetite deposition of 4 mg/cm2 (~4 grams/ft2)
Low chloride and silica contamination
The results provide support for treatment methods which permit low levels (generally
<1 ppm) of free caustic, such as equilibrium phosphate treatment under the tube
cleanliness conditions tested.
Work conducted by the Canadian Electrical Association(11) identified the sodium-iron
phosphate reactions that take place up to 360C. The major iron reaction products that
cause hideout (or more specifically in these experiments, uptake by magnetite at
Na/PO4 molar ratios near 2.5) were identified from batch experiments as NaFe++PO4
(maricite) and Na4Fe+++(OH)(PO4)2 1/3NaOH. At higher Na/PO4 ratios Na3-2xFex++
PO4 (a solid solution with Na3PO4) replaces maricite as the stable reaction product. At
360C (680F) uptake by magnetite behavior is similar except that there appears to be
no significant amount of iron (+2) reaction products with Na/PO4 ratios of 2.5 or
greater. If the Na/PO4 ratio is large (>3.5), no uptake by magnetite takes place.
Nickel (NiO) reportedly behaves similarly. The Na/PO4 ratio in boiler water required
to avoid the formation of more acidic phosphate mixtures (maricite + iron III phases)
increases from about 2.3 at 315C (599F) to about 2.7 at 360C (680F). The injection of
1-5

Introduction
solutions with Na/PO4 ratios above 3.0 causes little or no iron-containing phosphate
deposit to form at 360C (680F).
EPRI published a revised Guideline (12) for phosphate treatment for drum units which
took into account the results of all these studies and relevant utility experiences. This
has been accomplished by providing two phosphate treatments (see Figure 5-2): the
first, called phosphate treatment (PT), involves a broadening of the control range above
the sodium-to-phosphate 2.8 molar ratio curve and allows operation with up to 1 ppm
of free sodium hydroxide; the second, equilibrium phosphate treatment (EPT), operates
at or below phosphate levels which would lead to hideout. In high performance units
with low tolerance for phosphate, operation with up to 1 ppm of free hydroxide is
allowed. The major philosophy change incorporated has been to try to minimize or
eliminate phosphate hideout and the continual correction of the boiler chemistry by
addition of the acid phosphate chemicals (di, and mono-sodium phosphate). PT is
essentially an extension of EPT at higher phosphate levels. From a control viewpoint,
the major difference is in the level of allowed contaminants, which must be consistent
with the buffering capacity of the treatment in use. Since the guideline was introduced
in 1994, the incidence of corrosion has decreased markedly and utilities are able to
control the phosphate chemistry with minimum or reduced levels of hideout.
Operation with these new phosphate treatments allows cycling of the unit within
chemical control boundaries.
Deposition and Chemical Cleaning

Deposition has a very important influence on waterside failure mechanisms and
component performance. The deposition of feedwater corrosion products, and
particularly their minimization, on the waterwalls of the boiler is key to a successful
boiler treatment program. EPRI has recently initiated a strategic project to develop
quantitative understanding of deposition processes throughout the steam and water
cycle. In the interim there are a number of published documents, which relate to the
operation of an optimum cycle chemistry program(1215), to the minimization of
deposition(16, 17) and to the determination of the need to chemically clean a boiler(18).
Steam, Chemistry and Corrosion in the Phase Transition Zone (PTZ)

Recently EPRI published a State-of-Knowledge document in this area(16) which included
information on steam chemistry, moisture nucleation, early condensate and deposition
within the phase transition area of the steam turbine. This work led to the formation of
an international collaboration consisting of 23 organizations that are performing
detailed monitoring of these areas in operating turbines, and of extensive model
turbine studies of the PTZ. It is anticipated that the work will lead to a complete
understanding of the environment in the PTZ, which will ultimately provide better
1-6

Introduction
steam chemistry limits. It has already led to a better understanding of the importance
of providing a suitable shutdown environment to the low pressure turbine.
1.2 EPRI FOSSIL PLANT GUIDELINES AND MANAGEMENT APPROACHES

FOR CYCLE CHEMISTRY
Over the period 19931996, EPRI has incorporated the information from all the ongoing cycle chemistry projects into individual guidelines which are revisions of the
Interim Consensus Guidelines:
x
Phosphate treatment guidelines to cover phosphate treatment (PT) and equilibrium

phosphate treatment (EPT) for drum units(12)
Oxygenated treatment for once-through and drum units(14)
All-volatile treatment for once-through and drum units(15)
EPRI has also prepared a document(19) which summarizes the worldwide experience
with caustic treatment for drum boilers. This treatment is currently utilized
successfully in over 50,000 MW of drum boilers at applied concentrations up to 2 ppm
NaOH.
The Selection and Optimization of Boiler Water and Feedwater was published in
1997(21). This document is the glue which brings the four guidelines together; it helps
a utility to select the optimum treatment for specific units and provides a road-map
methodology to optimize the feedwater for all-ferrous and mixed metallurgy feedwater
systems.
In parallel to the guidelines development, EPRI has developed a very successful Cycle
Chemistry Improvement Program(13, 20) and has demonstrated it with nine utilities. This
includes the minimum level of instrumentation that all fossil plants are considered to
need (core parameters) and which was developed as a result of the monitoring
program(2) and international data(4). Table 1-1 shows these parameters/instrumentation
together with the diagnostic parameters, which should be used (a) in cases of
contaminant ingress or when target levels are exceeded (troubleshooting parameters),
and (b) during commissioning of cycle chemistry.
Also included in the CCIP is the optimum management approach for a utilitys cycle
chemistry program, and the methodology to record the costs/benefits of an improving
cycle chemistry.
1-7

Introduction
Table 1-1
Core Monitoring Parameters (Minimum level of instruments for all plants/units)
Parameters
Measurement Locations
Usage. On-Line/
Grab
Cation Conductivity x CP Discharge
O
Cation Conductivity x Polisher Outlet and Economizer O
Inlet
Cation
O
x Blowdown or Downcomer
2
Conductivity
Cation Conductivity x Hot Reheat Steam or Main
O
Steam
Dissolved Oxygen x CP Discharge
O
O
x Economizer Inlet
pH (Drum Boilers) x Blowdown or Downcomer
O
Sodium
O
x CP Discharge
Sodium
x Polisher Outlet or Economizer O
Inlet
Sodium
O
x Hot Reheat Steam or Main
Steam
Frequency
Measurement
C
C
C
C
C
C
C
C
C
C
Additional Monitoring or Diagnostic Parameters

Parameters
pH
Specific
Conductivity
Silica
Phosphate1
Measurement Locations
x Economizer Inlet
x Economizer Inlet
x Treated Makeup
x Treated Makeup
x Economizer Inlet
x Economizer Inlet
x Condensate Pump Discharge
Chloride
Iron
Copper
Total Organic
Carbon
Air In-leakage
x Air Removal System
ORP
x Economizer inlet and feedwater
1 Drum Boilers on Phosphate Treatments
2 Drum Boilers on AVT and OT
O - On-Line
G - Grab
1-8
Usage. On-Line/
Grab
2
2
2
2
2 or G
2 or G
G
G
G
2 or G
Frequency
Measurement
C
C
C
C
C or S
C or D
W
W
W
C or D
O or G
W
C - Continuous or Semi-Continuous
S - Grab, Once/Shift
D - Grab, Once/Day
W - Grab, Once/Week

Introduction
1.3 NEED AND DEVELOPMENT FOR

CYCLING/SHUTDOWN/STARTUP/LAYUP GUIDELINES
As can be seen from the previous discussion, there is now comprehensive coverage of
guideline limits for all operating chemistries and unit configurations. There is a
methodology to select and optimize the treatment for each specific unit. All the
necessary management approaches to run a successful cycle chemistry program are also
available.
Despite this, only rudimentary information on the effects of cycling, shutdown, startup
and layup on cycle chemistry and unit availability/reliability has been available. No
comprehensive guidelines exist. This has been well identified by the industry, but until
now the necessary information and underpinnings for such a guideline for chemists
and operators has not been available.
It is clear that improper shutdown and layup can lead to serious plant damage such as
pitting, oxidation and corrosion, which during operation can be the initiators of the
serious major failure mechanisms affecting plant availability. Two such important
mechanisms are: a) pitting in unprotected reheaters which can lead to multiple reheater
leaks, and b) pits on low pressure turbine blade/disk surfaces in the PTZ, which can be
precursors to stress corrosion cracking and corrosion fatigue.
A recent survey(22), conducted of over 60 utilities of their chemistry practices, provides
some important clues as to the extent of protection (or lack of it) applied to units during
shutdown. Some of the results include:
x
13% nitrogen blanket heaters.
35% nitrogen blanket boiler.
Very low % protect turbine during SD.
49% dont know the Fe and Cu levels on SU.
46% dont use deaerated water on SU.
40% put makeup directly into cycle.
66% put makeup into vented storage tank.
Hydrazine is most common scavenger (66%).
28% dont use scavenger during layup (this is normal and OK for OT units).
1-9

Introduction
x
Short term shutdown is biggest concern.
Damage due to cycling: BTF, condenser leaks, and LP blade problems
58% think guideline is high priority.

38% think it is urgently needed.
It is also well understood that the cycle chemistry can often be outside of guideline
limits during the startup period, and that the level of corrosion products, flowing from
the feedwater system and within the boiler, are highest during this period. Poor
shutdown and layup only exacerbate these problems. The choice of chemistry for a
unit is important, not only when the unit is operating, but also during the transient
conditions of shutdown and startup. For instance: the choice of OT over AVT for drum
and once-through units reduced markedly the level of corrosion products during
startup; the choice of EPT over CPT should remove the possibility of hideout and
hideout return during startup and shutdown respectively.
There has been much discussion about whether phosphate or caustic should be added
to a drum boiler during the startup period, either as an automatic addition or in
response to a contaminant.
These new guidelines assembled in this document address all these concerns.
1.4 OBJECTIVES OF THESE GUIDELINES

The overall objective of these guidelines is to minimize the impact of cycling and
peaking operation, and to achieve availability and efficiency similar to the base loaded
unit. Specific objectives are to:
x
Maximize unit life and minimize forced outages
Maximize power production and thermodynamic efficiency
Minimize scale formation and corrosion, and transport
Minimize impurity ingress, generation, and transport
Maximum unit life and low forced outage rate are achieved by a combination of control
of operating stresses, and chemistry of water and steam. High operating stresses are
mostly caused by temperature transients in heavy section components such as boiler
drums, superheater and reheater headers, and turbine rotors and casings. High
stresses are also produced in boiler waterwall tubes by heating, cooling, and circulation
problems. The above conditions can lead to low cycle fatigue, low cycle corrosion
fatigue, and stress corrosion cracking.
1-10

Introduction
In marginally designed highly stressed components, such as for example LP turbine

blade attachments, the stress cycling produced by frequent shutdowns can also reduce
corrosion fatigue life.
Corrosion caused by ingress of cooling water impurities and oxygen and carbon
dioxide which enter through air inleakage, reduces the useful life of all waterside and
steamside component surfaces.
High power production and efficiency is achieved by minimization of impurity ingress
which leads to generation and transport of iron and copper oxides. These oxides form
scale in boiler and feedwater heater tubes, reducing heat transfer. In the turbine, metal
oxides and salts form deposits which reduce the flow capacity and, through surface
roughness, reduce thermodynamic efficiency.
1.5 SCOPE OF THESE GUIDELINES

These guidelines cover the following steam cycles, water treatments, types of operation,
and pressure control:
x
Drum boiler units above 600 psi (4Mpa) drum pressure and once-through
subcritical and supercritical boiler units
Units with and without condensate polishers
All-ferrous and mixed metallurgy feedwater systems
Superheaters, reheaters and turbines
Water treatments: Phosphate treatment and equilibrium phosphate treatment, allvolatile treatment, oxygenated treatment and caustic treatment
Base load, peaking, and cycling operation
Constant and sliding pressure
1.6 REFERENCES
1. Interim Consensus Guidelines on Fossil Plant Cycle Chemistry. Electric Power Research
Institute, Palo Alto, Calif. CS-4629. June 1986.
2. Monitoring Cycle Water Chemistry in Fossil Plants: Volume 1, Monitoring Results.
Electric Power Research Institute, Palo Alto, Calif. EPRI GS-7556, Vol. October 1991.
1-11

Introduction
3. Monitoring Cycle Water Chemistry in Fossil Plants: Volume 3, Project Conclusions and
Recommendations. Electric Power Research Institute, Palo Alto, Calif. EPRI GS-7556,
Vol. 3, October 1991.
4. Monitoring Cycle Water Chemistry in Fossil Plants: Volume 2, International Water
Treatment Practices in Fossil Fuel Units. Electric Power Research Institute, Palo Alto,
Calif. EPRI GS-7556, Vol. 2. December 1992.
5. Behavior of Ammonium Salts in Steam Cycles. Electric Power Research Institute, Palo
Alto, Calif. EPRI TR-102377. Final Report. December 1993.
6. R.B. Dooley and S. Paterson, Phosphate Treatment: Boiler Tube Failures Lead to
Optimum Treatment. Proceedings: 55th International Water Conference. Engineers
Society of Western Pennsylvania. 1994.
7. R.B. Dooley and W.P. McNaughton, Boiler Tube Failures: Theory and Practice. EPRI
Book TR-105261. 1996.
8. S.L. Goodstine and R.B. Dooley, Behavior of Sodium Phosphates Under Boiler
Conditions. Proceedings: 54th International Water Conference. Engineers Society of
Western Pennsylvania. 1993.
9. Behavior of Sodium Phosphate Under Boiler Conditions. Electric Power Research
Institute, Palo Alto, Calif. TR-102431. June 1994.
10. P. Goldstein and C.L. Burton, A Research Study on Internal Corrosion of High
Pressure Boilers Final Report. Transactions of the ASME, Journal of Engineering for
Power. April 1969.
11. P.R. Tremaine, L.G.S. Gray, B. Wiwchar, P. Taylor and J. Stodola, Phosphate
Interactions with Metal Oxides Under High Performance Boiler Hideout
Conditions. Proceedings: 54th International Water Conference. Engineers Society of
Western Pennsylvania. 1993.
12. Cycle Chemistry Guidelines for Fossil Plants: Phosphate Treatment for Drum Units.
Electric Power Research Institute, Palo Alto, Calif. EPRI TR-103665. Final Report.
December 1994.
13. Cycle Chemistry Corrosion and Deposition: Correction, Prevention and Control. Electric
Power Research Institute, Palo Alto, Calif. TR-103038. Final Report. December
1993.
14. Cycle Chemistry Guidelines for Fossil Plants: Oxygenated Treatment. Electric Power
Research Institute, Palo Alto, Calif. EPRI TR-102285. December 1994.
1-12

Introduction
15. Cycle Chemistry Guidelines for Fossil Plants: All-Volatile Treatment. Electric Power
Research Institute, Palo Alto, Calif. EPRI TR-105041. April 1996.
16. Turbine Steam, Chemistry, and Corrosion. Electric Power Research Institute, Palo Alto,
Calif. EPRI TR-103738. August 1994.
17. R.B. Dooley, J. Mathews, R. Pate and J. Taylor, Optimum Chemistry for AllFerrous Feedwater Systems: Why Use an Oxygen Scavenger?. Proceedings: 55th
International Water Conference. Engineers Society of Western Pennsylvania. 1994.
18. Guidelines for Chemical Cleaning of Fossil-Fueled Steam Generating Equipment. Electric
Power Research Institute, Palo Alto, Calif. TR-102401. Final Report. June 1993.
19. Sodium Hydroxide for Conditioning the Boiler Water of Drum-Type Boilers. Electric
Power Research Institute, Palo Alto, Calif. TR-104007. January 1995.
20. Cycle Chemistry Improvement Program. Electric Power Research Institute, Palo Alto,
Calif. TR-106371. April 1997.
21. Selection and Optimization of Boiler Water and Feedwater Treatments for Fossil Plants.
Electric Power Research Institute, Palo Alto, Calif. TR-105040. March 1997.
22. Proceedings: Fifth International Conference on Fossil Plant Cycle Chemistry. Edited by
R. B. Dooley and J. Mathews. Electric Power Research Institute, Palo Alto, Calif.
TR-108459. November 1997.
1-13
2
METALLURGICAL, DESIGN, AND OPERATING
CONSIDERATIONS
2.1 INTRODUCTION
In this Section, general and specific considerations relating water and steam chemistry
and steam cycle design and operation to corrosion and deposit formation are discussed.
Water chemistry, metallurgical, design, and operating aspects are combined because
they all strongly interact, particularly in cycling units.
Operator and chemist actions influence the generation, cycle transport, and removal of
corrosion products and ingress of impurities. Designers, operators, and chemists
influence the impurity concentration on heat transfer and turbine surfaces. Control of
stresses and the number of stress cycles which interact with the chemistry in producing
equipment damage (corrosion fatigue, stress corrosion, etc.) is by operation and design.
In Section 2.1 - Introduction, the impurity generation, transport, and corrosion effects,
and steam cycle materials are described. The basics of material corrosion and cycle
component mechanisms are given in Section 2.2, differences between the all-ferrous vs.
copper-containing preboiler systems are outlined in Section 2.3, priorities for transient
operation in Section 2.4, and the effects of steam cycle component design and operation
are discussed in Section 2.5. A brief assessment of the alternative water treatment
chemicals is presented in Section 2.6.
The steam cycle startup and cycling sequence may cover all or some of the following
main steps:
x
shutdown
short or longterm layup
system draining and filling
water cleanup before firing
2-1

Metallurgical, Design, and Operating Considerations
x
boiler firing and warmup
steam turbine bypass operation
turbine roll and warmup
turbine speed ramp with holds
synchronization
load ramping
All the above steps involve water chemistry considerations and control limits and
equipment considerations relating to thermal stresses, resonant speeds for rotating
machinery, deaeration, water hammer and water induction, rubbing and cavitation of
pumps, and other concerns. Schematically, the philosophy of the three legs of a
milking stool supporting reliable operation applies (see Figure 2-1) even more to
transient operation than to base load.
d
n
f water a
Control o emistry
steam ch
Failure resistant materials
Control o
f stress
Cycling operation
Figure 2-1 Three supports for reliable cycling operation
While these guidelines concentrate on water and steam chemistry, the main emphasis
for operators of the startup and cycling operation is on the control of thermal and
vibratory stresses which can interact with the environment and result in corrosion
cracking (corrosion fatigue and stress corrosion).
2-2

Impurity Generation, Transport, and Corrosion Effects

To minimize impurity ingress, generation, and transport, the sources of impurities,
effects of layup, and the startup, shutdown, and operational chemical transport
characteristics of each cycle should be periodically determined during commissioning
and thereafter about every five years(1-6). Important characteristics which need to be
recognized include:
x
oxidation of cycle materials and deposited copper during layup
precipitation of suspended solids in feedwater and boiler water due to changing

pH, O2, redox potential, and temperature during layup and startup
introduction of aerated (O2 + CO2) makeup from storage tanks during system fill
and from the deaerator storage tank during startup
deaeration in the condenser and deaerator
boiler carryover and drum level control
transport of exfoliated oxides into the turbine and around the cycle
transport of metal oxides from dead legs and mud drums
sloughage of impurities from condensate polisher resins
Typical water chemistry and corrosion effects of layup, startup, and cycling are
illustrated for a drum boiler cycle in Figure 2-2 and Table 2-1. Figure 2-3 is a summary
of the sources of contaminants, most of them active during startup and cycling. In
particular: air inleakage, corrosion and exfoliation products, condenser leaks, aerated
makeup water from storage tanks, condensate polishers, and, sometimes, the
combustion products entering leaking reheater tubes (and via this route to the IP and
LP turbines) during initial firing when the reheater is under vacuum. Figure 2-4 shows
the steam cycle components and thermodynamic conditions where various impurities
can cause corrosion. These regions change with load and during shutdown and
startup.
2-3

high carry-over due to
drum level control and
suspended solids
IP
turbine
HP turbine
System
filled with
aerated
water
pH and
redox
changes
lead to
dissolution,
precipitation,
and
deposition
of oxides
LP
turbine
Condenser
Deaeratorgood deaeration
at all loads
HP heaters
NH3 + O2 + CO2
- Poor deaeration
- Corrosion of
Cu alloys
Makeup
Attemperation
Boiler
Turbine:
Pitting during layup
Washing of
deposits
LP heaters
Fe fouling
and rapid
exhaustion
by CO2
Condensate
polisher
High Fe, Cu into

boiler during
startup
Impurity ingress
Corrosion
Deposition
Cu alloy and C-Steel oxidation during layup

Oxide transport and deposition during startup
Figure 2-2 Typical water chemistry and corrosion effects of layup, startup and
cycling for a drum boiler cycle
2-4
ea
rl
ks
rod
ge
in le
ts
duc
Maintenance
Design
rs
pro
Air
ion
Reheater
maintenance
Selection of
chemicals
ica
Control of
l cl
ea
nin cleaning
g
em
ros
aka
mb
Ch
Cor
t
us
p wate
Makeu
Water
and
steam
p
ion
Co
Co
*
ts
uc
Resin testing
Monitoring
Nitrogen sparging
of storage tanks
*
*
Pain
preservts, solvents,
atives,
etc.
QC: Maintenance
Purchasing
he
lis
po
se
te
en
sa
nd
en
Co
Design, Materials
Preventive
maintenance
Monitoring
Regeneration
Design
Resin testing
monitoring/
operation
nd
Selection of
treatment
QC-Purchasing
Water treatment chemicals
Material selection
Avoid copper
Water chemistry
Design
Exfoliation
Figure 2-3 Sources of contaminants enhanced by cycling operation and examples

of engineering solutions.
2-5
ine
Sup
r
ate
erh
eat
er
Re
he
HP
t
u rb
IP turbine
Caustic stress
corrosion cracking
Boiling and high
heat flux zones
Na O
LP turbine
Hs
olu
tio
ns
Pitting, stress corrosion
cracking, corrosion fatigue
(Causes: Cl, SO4, CO3 O2,
CuO, Acetate,...)
30% NaCl solut
ions
Salt zone
turationCline
Sa
o rro
sio
(Causes n-ero
:C
sio
O
n
low pH
, h ig 2 , a c
ids
hv
,
elo
c it
y)
Wa
ter
dro
ple
te
ro s
ion
20% Moisture
4%
Boi
ler
fe Ex
ed tra
wa ct
te ion
rh s
ea to
te
rs
6%
8%
10%
12%
se
n
de
G
e
of ner
ca al
rb co
on rro
st sio
ee n
l
n
sio 2)
rr o + O
o
r c NH 4
e
pp es
Co aus
(c
20%
Co
T
P
Superheat
Enthalpy
50%
Entropy
70%
Note: This diagram illustrates regions where impurities will concentrate and promote corrosion. Points in the diagram
should relate to actual conditions at component surfaces, not to the theoretical average flow path conditions. Heat
transfer, surface cleanliness, crevices, and surface-flow stagnation conditions determine the actual surface
temperatures and pressures.
Figure 2-4 Mollier diagram for a fossil cycle
2-6
EPRILi
censedMateri
al
Met
alurgical
,Design,andOperat
i
ngConsiderat
i
ons
T
bn
lsi
2
1tEfectsandThei
Tra
en
rAmel
i
orat
i
on
Transient Effects
How to Reduce the Impact
Unprotected cycle components corrode

during layup. Layup generated oxides are
transported during the startup sequence
around the cycle (see Figure 2-2).
Proper layup, startup cleanup,

condensate polishing or filtration,
drain and fill, washing condenser
with turbine hood spray.
If not removed, these oxides deposit in the

feedwater heaters and the boiler and some
can be carried with attemperating sprays
into the superheater and reheater and the
turbine.
Boiler blowdown, feedwater cleanup

(may need to retrofit cleanup loops,
turbine bypass).
pH, oxygen, and temperature changes cause

dissolution and precipitation of metal oxides
on boiler tube and other surfaces (see Figures
2-6 to 2-9).
Maintain proper boiler water and

feedwater pH, fill with deaerated
water.
The presence of salt deposits in the turbine

and humid air cause pitting corrosion.
Turbine layup with dehumidified air

or nitrogen, turbine washing.
An increase of air inleakage during low load

operation introduces oxygen and carbon
dioxide, which can lead to general and
pitting corrosion; carbonic acid can influence
flow accelerated corrosion.
Fix air inleakage.
The efficiency of deaeration in the condenser

is poor during low load operation.
Improve condenser deaeration by

steam sparging, additional air
ejectors or vacuum pumps.
Carbonate generated from the CO2 which

entered the cycle during startup and low load
operation, and the aerated makeup from the
deaerator storage tank and boiler fill act as an
eluent, replacing the already exchanged
anions on the condensate polisher resin.
Fix air inleakage, fill with deaerated

water (pegging steam to deaerator,
nitrogen blanketing and sparging of
condensate storage tank)
2-7

High transient stresses in heavy section

components resulting from temperature
transients, stresses in boiler water wall tubes
resulting from irregular circulation, and
vibration resonance and increased alternating
stresses in the rotating equipment interact
with marginal water and steam chemistry
producing accelerated stress corrosion and
corrosion fatigue crack propagation.
Follow vendor instructions for

startup and cycling, retrofit cycling
designs and controls, maintain good
water and steam chemistry.
During shutdown, exfoliation of superheater,

reheater, and steam pipe oxides occurs,
leading to solid particle erosion in the HP
and IP turbine during the subsequent startup,
and transport and deposition of magnetite
around the cycle.
Minimize the rate of metal

temperature changes, remove
exfoliated oxides through main
steam drains, use condensate
polishers and/or filters.
Superheater and reheater corrosion due to

wetting of previously deposited salts.
Optimum is to use dehumidified air

for prolonged off-load periods.
However, wet protected storage can
also be used (see Figure 4-8)
Hideout and hideout return of many

chemical impurities and additives occurs
during transients.
Optimize phosphate control, keep

boiler, superheater, and reheater
clean, use condensate polishers.
Steam Cycle Materials and Their Properties

In fossil utility cycles, the steam cycle component materials which need to be protected
by the chemical treatment and during layup, include carbon steels, austenitic and
ferritic stainless steels, and copper alloys. These common materials can be subject to
corrosion damage during operation and layup. They can be attacked by the
concentrated impurities formed in steam cycles, by hot water and steam, and by a
combination of humid air and corrosive deposits during layup.
Typical materials for the key cycle components are:
Boiler: carbon and low alloy steels
2-8

Superheater and reheater: carbon, low alloy and austenitic stainless steels
Steam piping: low alloy or carbon steel
Turbine: low alloy steels for rotors and HP and IP cylinders, ferritic stainless
steels and titanium alloys for blades, austenitic stainless steels for stationary
blades, super alloys for high temperature bolting
Feedwater heaters and condensers: carbon steel for shells and feedwater heater
tubing, austenitic and ferritic stainless steels, titanium, and copper alloys for
feedwater heater and condenser tubing
Feedwater piping: carbon steel, low alloy and stainless steels for sections
susceptible to FAC
Material Properties
For the evaluation of the effects of cycling on steam cycle components, mechanical,
fracture, fatigue, creep, and corrosion properties need to be known(6-26). These
properties must cover behavior of smooth and notched surfaces, materials with and
without defects, and crack propagation behavior under fatigue and corrosion cracking
conditions.
New materials have been developed for replacement of the components, the life of
which has been exhausted and for the retrofits for cycling service. These have better
fracture, fatigue, and creep properties.
2.2 STEAM CYCLE COMPONENT CORROSION AND DEPOSITS

During cycling and other transient operation, the corrosion situation in steam cycles is
aggravated by increased steady and vibratory stresses (corrosion cracking) and often by
marginal water and steam chemistry, i.e., ingress of air, system filling with aerated
water, transport of corrosion products, washing of deposited impurities, chemical
hideout, fast exhaustion of condensate polishers, condenser leaks (particularly during
startups), etc.
Basics of Material Corrosion

The cycle materials can be subject to many corrosion mechanisms including:
x
general corrosion, and high temperature steam oxidation
galvanic corrosion
2-9

x
stress corrosion
low cycle and high cycle corrosion fatigue
crevice corrosion
pitting
flow-accelerated corrosion (erosion-corrosion)
exfoliation
fretting
Where in the steam cycle these mechanisms are active depends on the thermodynamic
and flow conditions, water and steam chemistry (see Figure 2-4), materials, and
stresses. Corrosion data can be found in hundreds of technical papers, EPRI reports,
and book compilations(15, 23-26).
General Corrosion - is the most important for: a) carbon steels which are used for boiler
tubes, feedwater piping, pressure vessel shells, turbine casings, condenser shell, and
feedwater heater tubing, and b) for copper alloys, which are used for condenser,
feedwater heater, and auxiliary heat exchanger tubing. General corrosion is affected by
the chemistry at the metal surface; most significantly by oxidizing-reducing potential
(redox), pH at temperature, oxygen, and concentrated salts, acids, and hydroxides. It is
also exponentially dependent on temperature. Typical relationships for corrosion of
carbon steel are given in Figures 2-5 and 2-6. Selected corrosion data for copper alloys
are shown in Figures 2-7 to 2-9. For an evaluation of the effects of the corrosive
environment, the conditions at the surface, including impurity concentration, corrosion
potential, and temperature, must be considered (Figure 2-4).
2-10

Potential (Driving Force for Corrosion) (volts)
Stable Species at 300C

Metallic iron
Hematite (Fe2O3)
Magnetite (Fe3O4)
0.5
Passivation
0
Normal boiler
operating range
-0.5
Acid
corrosion
-1.0
Immunity
Alkaline
corrosion
4
Acid
6
8
Neutral
pH
10
12
Alkaline
14
Figure 2-5 Potential - pH diagram for carbon steel in 300 C water(19)
2-11

Solubility, mmol/kg: Corrosion Rate, mm/year
Corrosion
Linear
Fe(OH)42-
Magnetite
solubility
101
100
Fe2+
Linear
10-1
Fe(OH)3-
10-2
Fe(OH)+
Cubic
Parabolic
10-3
10-4
Fe(OH)2
10
12
pH 300C
100
10-2
10-4
10-4
Conc. HCl, mol/kg
10-2
100
Conc. NaOH, mol/kg

Neutral
Figure 2-6 Corrosion of mild steel and solubility of magnetite at 300C, showing
corrosion rate laws(15,20.21)
2-12

Potential, V(H)
0.6
Cu++
CuO
0.4
++
Cu(NH3)4
Cu2O
CuO
0.2
Cu(NH3)2
-0.2
Cu2O
Cu
-0.4
-0.6
0
8
pH
10
12
14
16
Figure 2-7 Potential - pH diagram for copper in ammonia solutions at 25C(22)
2-13

Copper Release (ppb )
30
CDA-706. (Cu/Ni: 90/10),

274F, hydrazine added
28
CDA-706, 375F,
hydrazine added
26
SoMs 71 brass, 86F,
alkalized with NH3
24
CDA-443 (Admiralty brass),

193F, hydrazine added
22
Aluminum brass,
temperature unknown
20
18
16
14
12
10
8
6
4
2
0
8.5
9.0
pH at 25C
9.5
Figure 2-8 Average copper release as a function of pH

Adapted from Corrosion-Product Transport in PWR Secondary Systems, EPRI NP-2149,
December 1981, and Effects of Hydrazine and pH on the Corrosion of Copper-Alloy Materials
in AVT Environments with Oxygen, EPRI NP-2654, December 1982.
2-14

Corrosion Product Release Rate, g/m2 yr
50.0
20.0
10.0
5.0
70Cu/30Ni
2.0
1.0
90Cu/10Ni
0.5
0.2
0
10
pH
Figure 2-9 Effect of pH on steady state release rates for 90Cu/10Ni and 70Cu/30Ni
exposed to ammonia solutions containing 8-21 g/kg oxygen, flowing at ~1ft/s
(0.3m/s) and at a temperature of 35 - 38C(22)
Corrosion Fatigue - depends on stress or strain amplitude, mean (or average) stress,
(15,18,24)
. Pitting can significantly reduce the
and the environment, including temperature
time for crack initiation and failure. An example of the effect of environment on
corrosion fatigue is shown in Figure 2-10 which is a corrosion fatigue diagram for LP
turbine disk and rotor steel(18).
The 45 line represents the mean stress line or no alternating stress. The farther the data
falls away from the mean stress line, the higher the alternating stress that can be
withstood for a given mean stress and stay below the fatigue strength of the material.
Agressive environments (increasing NaCl) represented by the lines below the 45 line,
and high mean stresses lead to marked acceleration of corrosion fatigue cracks.
Corrosion fatigue of carbon steel tubing used for boiler waterwalls has been extensively
investigated(25) and strong effects of off-limit boiler water chemistry (pH, oxygen) on
crack initiation and propagation were found.
2-15

Alternating Stress, m6a, (MPa)

600
500
Air
ns
400
io
dit
e
vic
co
300
Se
200
100
100
-200
-300
0
100
200
300
400
Mean Stress, m, (MPa)
500
600
Figure 2-10 Corrosion fatigue diagram for NiCrMoV

LP turbine disk and rotor steel18
Stress Corrosion Cracking (SCC) - is a corrosion damage mechanism resulting from a

combination of high tensile stress and environment. The tensile stress can be an
operating stress or a residual stress, such as residual welding stress. SCC is also
strongly temperature dependent. Sodium hydroxide is a common steam cycle impurity
which has the strongest effect on stress corrosion, however, other impurities such as
acids and salts can also induce SCC. For higher strength materials, such as the LP
turbine disk low alloy steels, even pure water and wet steam can cause cracking. An
example of stress corrosion behavior is shown in Figure 2-11, which shows the
dependence of the threshold stress VSCC, threshold stress intensity KISCC, and stress
2-16

corrosion crack propagation rate (da/dt) on yield strength for an LP turbine disk
material(18).
10-5
100
600
60
40
500
SCC
400
10-7
300
KISCC
20
da/dt, mm/s
80
SCC, (MPa)
KISCC MPa m1/2
10-6
10-8
da/dt
200
10-9
400
500
600 700 800 900 1000 1100 1200

Yield Strength (0.2%), MPa
Figure 2-11 Stress corrosion of NiCrMoV disk steel vs. yield strength for "good"
water and steam(18)
Cycle Component Damage Mechanisms

Startup and cycling operation often lead to acceleration of corrosion and other damage
mechanisms of steam cycle components. This is because there are increased thermal
and vibratory stresses at the same time as when water and steam chemistry are
marginal, and because the corrosion products generated during layup are transported
and deposited around the cycle.
Major damage mechanisms influenced by cycle chemistry and the effects of startup and
cycling are listed in Tables 2-2 to 2-4, expanded from reference 27.
2-17

Table 2-2
Boiler Tube Damage Mechanisms Influenced by Cycle Chemistry (Adapted from
reference 27) (Discussion of each mechanism can be found in Reference 25)
Mechanism
Chemistry Influence
Effects of Cycling
Corrosion fatigue
Poor water chemistry, shutdown or

layup practices, and improper chemical
cleaning (with HCl) worsen the
contribution of the damage-causing
environment
Marginal chemistry,
circulation
problems in natl.
circ. boilers, thermal
stresses
Hydrogen damage
Excessive deposits from feedwater

corrosion products combined with
contamination by acids or salts
Marginal chemistry,
deposition of oxides
Caustic gouging
Excessive deposits from feedwater

corrosion products combined with
caustic contamination
Hideout, dirty tubes
Fireside corrosion
Mechanism accelerated by increased

metal temperatures resulting from
excessive tube deposits
Tube deposits
Short- and longterm overheating
Increased tube metal temperatures

resulting from excessive deposits; orifice
plugging by feedwater corrosion
products prevents cooling
Dirty tubes,
circulation
Flow-accelerated
corrosion of
economizer
Reducing conditions and low pH

feedwater
CO2 + low pH
Pitting in
economizer
Stagnant, oxygenated water during

shutdown
Layup
Pitting in reheater
Concentration of salts or H2SO4 at lower

bends during layup; carryover or flue
gas
More frequent salts

+ condensed steam
+ air
2-18

Table 2-3
Turbine Deposits & Damage Mechanisms Influenced by Cycle Chemistry (Adapted from
reference 27) (Discussion of each mechanism can be found in Reference 65)
Mechanism
Chemistry Influence
Effects of Cycling
Stress
corrosion
cracking of LP
disks, rotors,
HP bolts, ...
Excessive corrodents present in steam,

and drying of liquid films and moisture
combined with synergistic effects of
tensile stress and materials, deposition
of corrodents
Pitting during
unprotected layup
accelerates SCC,
marginal startup
chemistry
High cycle
corrosion
fatigue of LP
blades and
disks
Excessive corrodents present in steam

combined with cyclic stresses
Pitting during
unprotected layup
accelerates CF, rotating
machinery through
critical speed - vibration
Low cycle
corrosion
fatigue
Deposited corrodents, particularly

NaOH
Pitting during
unprotected layup, stress
and strain cycling due to
startups and thermal
stresses
Pitting
Salts or acidic corrodents in steam,

unprotected layup - create sites of SCC
or corrosion fatigue
Deposited salts during

unprotected layup
HP blade
deposits
Copper in steam deposits on HP blades

and nozzles decreasing efficiency and
MW output
Copper alloys and

deposited copper oxidize
during unprotected
layup, transport during
startup
Silica deposits
on LP blades
Precipitation of silica in steam excessive deposits lead to partial

pluggage of seals, mis-operation of
valves, deformation of blades and
diaphragms and efficiency losses
Marginal startup
chemistry
Solid particle
erosion - HP,
IP
SH and RH tube exfoliation is not

influenced by chemistry, but causes Fe
loading during startups
Exfoliation during
shutdown, transport
during startup
2-19

Table 2-4
Condensate/Feedwater Cycle Damage Mechanisms Influenced by Startup Cycle
Chemistry (Adapted from reference 27)
Location
Mechanism
Condensate
and feedwater
systems
Carbon steel and

copper alloy
corrosion and
corrosion product
transport
Low pH, acid constituents, excess carbon

dioxide and oxygen present in condensate;
alternating oxidizing and reducing
conditions, excess hydrazine solubilizing
magnetite
Heater drain
and feedwater
piping
Flow-accelerated
corrosion (FAC) of
carbon steel
Attack by reducing feedwater conditions

and high velocities, excessive hydrazine
with "zero" oxygen, low pH
Copper alloy
condenser and
heater tubes
Ammonia
attack/condensate
corrosion
Simultaneous excess ammonia, oxygen, and

CO2 in steam synergistically oxidizing and
solubilizing copper
Feedwater
heater tubes
Stress corrosion
cracking Cu/Ni,
Monel, Stainless
Steel
Excessive corrodents in steam synergistic

with tensile stress, corrodent concentration
in crevices, dry - wet transition
Condenser
and heater
tubes
Admiralty Brass
stress corrosion
cracking
Excessive ammonia/chloride present in

steam synergistic with residual stress at
tubesheets and in u-bends
Feedwater
heater tubes
Copper/nickel
exfoliation
Excessive oxygen on shutdown combined

with thermal cycling and thermal stresses
2-20
Chemistry Influence

2.3 PREBOILER SYSTEMS - ALL FERROUS VS. MIXED METALLURGY

The concerns with the pre-boiler systems for cycling duty include:
x
reliability of components (see Table 2-4)
generation and transport of corrosion products(3-6,15,22)
deaeration (see Section 2.5)
The generation and transport of corrosion products (iron, copper, nickel, and zinc
oxides) can cause boiler waterwall tube scale accumulation which can lead to tube
failures and turbine deposits which can lead to MW and efficiency loss. Copper
transport and accumulation in the superheater can act as a continuing source of copper
for the turbine.
The high pressure drum boiler utility units with all-ferrous metallurgy (no copper
alloys in feedwater heaters) usually have better efficiency and reliability than the
similar units with mixed metallurgy. It has been concluded that copper alloys should
not be used for the heat exchanger tubing applications in steam cycles(22). The main
water treatment dilemma is that there are different pH requirements for the control of
general corrosion and flow-accelerated corrosion for carbon steel and copper alloys.
Figure 2-12 shows that the feedwater pH for the best protection of carbon steel against
general corrosion under deoxygenated reducing conditions should be above 9.4, but for
the protection of copper/zinc alloys, below 9.1.
Other than using an oxidizing cycle where the oxidizing-reducing potential, ORP >
0mV the optimum protection of carbon steel against flow-accelerated corrosion (FAC) is
with pH>9.6 and oxygen concentration about 10 ppb. While to minimize copper
corrosion, excess hydrazine is required (ORP < 0mV), which may further accelerate
FAC of carbon steel.
Auxiliary Heat Exchangers - such as the hydrogen cooler and gland steam condenser
should be considered when deciding on feedwater control because they may contain
copper alloys even while the feedwater system does not.
Layup - practices are very important for protection and corrosion product generation
for both ferrous and copper alloy materials (see Section 4).
2-21
12
12
10
10
Copper
Iron
8.5
8.7
Copper as ppb Cu
Iron as ppb Fe
8.9
9.1
9.3
pH (25C)
9.5
9.7
9.9
Figure 2-12 The effect of pH on iron and copper concentration at the economizer
inlet. Source: D. Frey, Mechanics of Corrosion Product Formation and
Transport(14)
All-Ferrous Feedwater Systems(3, 4)

The corrosion behavior of all-ferrous feedwater systems depends on the materials used
for the condenser and feedwater heater tubing, feedwater chemistry, and local flow
conditions. Where only carbon steels and ferritic stainless steels are used, slightly
elevated oxygen concentration levels can reduce iron oxide generation. However,
where austenitic stainless steels are used, interaction of oxygen and chloride ions must
be considered in controlling feedwater and steam chemistry, particularly during
transients, because these materials are susceptible to pitting and stress corrosion
cracking.
In units with condensate polishing, austenitic stainless steels can tolerate higher oxygen
levels because the chloride in feedwater can be better controlled than in the units
without condensate polishers.
In an attempt to reduce feedwater corrosion products, the older operating guidelines55
(including EPRI's Interim Consensus Guidelines(1)) indicated that the feedwater oxygen
2-22

levels should be less than 5 ppb. Reduction of air inleakage did not always markedly
change the key indicators of preboiler system corrosion, such as the time between
chemical cleans; this indicates that this philosophy did not produce a serious reduction
in feedwater corrosion products. In the same time period, utilities have been adding,
increasing, and changing oxygen scavengers. The result has generally been a reduction
in economizer inlet oxygen levels and a concomitant oxygen scavenger increase. This
results in severe reducing conditions (oxidizing-reducing potentials of less than -350
mV) in the feedwater leading to an increase in feedwater corrosion products in allferrous systems: the opposite result to the initial consideration.
Table 2-5 provides an indication of the typical areas suffering from corrosion and flowaccelerated corrosion, and generation of feedwater corrosion products, and the major
cycle problem areas.
Table 2-5
Generation of Feedwater Corrosion Products by Corrosion and Flow-Accelerated
Corrosion, and the Major Unit Transport and Deposition Problem Areas for AllFerrous Systems
Generation
Low/high pressure heater tubes and
shells and drains
Deaerator
Economizer Inlet
Feedwater Piping
Transport and Deposition

Boiler deposits and increased boiler
pressure drop
Ripple magnetite formation on the
waterwalls of once-through units
At least five boiler tube failure mechanisms
affected by deposits
Frequent need for chemical cleaning
of boiler
Boiler feedpump fouling
Orifice fouling/plugging can lead to boiler
tube failures by overheat (creep)
For all-ferrous systems with excellent feedwater chemistry, it is clear from the past
experience that the optimum feedwater chemistry involves a transition to more
oxidizing conditions and a recognition that oxygen scavengers may not be needed(66),
and that higher dissolved oxygen levels can eliminate flow-accelerated corrosion. The
initial steps involve gradually eliminating the oxygen scavenger under controlled test
conditions(3), with the ultimate benefit accruing from the use of oxygenated treatment(30).
This treatment has been applied to hundreds of once-through boiler units and
numerous drum boiler units. This direction is reflected in Sections 3 and 4 of the new
EPRI AVT Guidelines(31) where it is suggested that oxygen levels should not be allowed
to drop below 1 ppb in units with all-ferrous feedwater systems.
2-23

The selection and optimization of feedwater treatment for all-ferrous systems is

discussed in detail in Section 4 of the Selection and Optimization Document(3).
Mixed Metallurgy Feedwater Systems (Copper Containing)(3, 4, 22, 28)

Mixed metallurgy feedwater systems are more common in drum boiler units where, in
high pressure units, the carryover of copper oxides can cause a loss in generating
capacity and efficiency due to turbine deposits. In once-through boiler units, copper
alloys may be used for condenser tubing only and the copper induced problems are
less frequent. Once-through systems also have condensate polishing which aids in
copper corrosion product removal.
As shown in Figure 2-12, it is difficult and sometimes impossible to control corrosion of
both carbon steel and copper alloys in the preboiler cycle. All copper alloys used in LP
and HP feedwater heaters corrode, and there is also the effect of temperature and flow
velocity.
Besides the corrosion of copper alloy feedwater heater and condenser tubing, the main
problem is deposition of copper and its oxides on the inlet stages of high pressure
turbines. This results in rapid loss of the MW generating capacity and turbine
efficiency, requiring chemical or mechanical cleaning of the turbine. Copper alloy
corrosion is aggravated by higher air inleakage during cycling operation. Both, oxygen
and carbon dioxide from air accelerate the corrosion. Significant ingress of air occurs
when the feedwater and boiler are filled with aerated water prior to a cold startup. The
practice of boiling out the ammonia and hydrazine dosed boiler layup water during
startup can produce a large quantity of copper corrosion products by the corrosion
attack of ammonia on condenser and feedwater heater tubes.
Additional problems caused by copper transport around the water and steam cycle
include: deposition on waterwall tubes and more complicated chemical cleaning and
aggravation of corrosion of cycle components by the deposited copper, nickel, and zinc
oxides (on boiler tubes, turbine blades, and austenitic stainless steel tubing). Table 2-6.
provides an indication of typical areas suffering from corrosion and flow-accelerated
corrosion, and generation of feedwater corrosion products.
2-24

Table 2-6
Generation of Feedwater Corrosion Products by Corrosion and Flow-Accelerated
Corrosion, and the Major Unit Transport and Deposition Problem Areas for Mixed
Metallurgy Systems
Generation
Transport and Deposition
Low/high pressure heaters,

Condenser
HP turbine deposits leading to MW loss

Boiler deposits and increased boiler pressure drop
At least five boiler tube failure mechanisms
Frequent need for chemical cleaning
Orifice fouling
Superheater deposits
Copper Transport
Transport of copper into the turbine occurs both during startups and normal operation.
Feedwater concentration of copper and its oxides (mostly as colloids) during cold
startup can be as high as 10 ppm. Depending upon the copper alloys used in the cycle,
there is also an elevated concentration of nickel and zinc.
These feedwater corrosion products deposit in the boiler and, after concentration in the
boiler water, are carried over into steam as mechanical and vaporous carryover.
Volatility of copper oxides at high boiler pressures (>2400 psi (17Mpa)) is very high,
and up to 30% of boiler water copper can be carried over into the main steam. Because
of this carryover, hundreds of pounds of copper can be deposited in superheaters and
slough-off and exfoliate. The third mode of copper transport into the turbine is by
attemperating sprays.
Minimization of the negative effects of copper can be achieved by replacement of
copper alloy tubing, prevention of corrosion during inactive periods by proper layup of
heaters and boilers, filling with deaerated water, stringent control of air inleakage, use
of condensate polishers, and control of oxygen in makeup water, particularly during
startups. The key feature here is to keep the environment reducing (ORP < 0mV)
during all periods of operation and shutdown(22).
Layup - After years of corrosion of copper alloys, the corrosion products are
transported and deposited throughout the steam cycle, including heaters, boiler,
superheater, and the turbine. The deposited copper is often in the form of metallic
copper and cuprous oxide (Cu2O), because during operation there is a reducing
environment. During an unprotected layup, these deposited species may oxidize to
cupric oxide (CuO) which can then be dissolved and transported downstream.
2-25

The selection and optimization of feedwater treatment for mixed metallurgy systems is
discussed in detail in Section 4 of the Selection and Optimization Document(3).
For mixed metallurgy systems, it is clear that reducing conditions (excess oxygen
scavenger) are required for the non-ferrous materials(22). The EPRI AVT Guidelines(31)
suggest that oxygen levels should be kept below 5 ppb at the economizer inlet.
However, the most appropriate oxygen scavenger concentration and residual oxygen
level can only be determined by carrying out a series of tests. (See road map in Section
4, Ref. 31 for mixed metallurgy feedwater systems.)
Because the copper alloy corrosion is caused by ammonia, oxygen, and ammonium
carbonate and bicarbonate, other amines have been tried and also other oxygen
scavengers besides hydrazine (because hydrazine decomposes into ammonia).
However, these efforts were not successful in high pressure units, because the alternate
(organic) chemicals decompose, forming organic acids and CO2 which are also
corrosive.
2.4 PRIORITIES FOR TRANSIENT OPERATION

The operation and controls related to safety and mechanical damage of equipment have
priority over the water and steam chemistry control steps. However, it should be
realized that some damage mechanisms, such as corrosion fatigue and stress corrosion
cracking, are the result of an interaction of mechanical stresses with the environment.
Also, there are high impact catastrophic failures such as LP turbine disc burst due to
stress corrosion cracking, deaerator failures, and piping failures due to flow-accelerated
corrosion which often occur during transients when a component, weakened by the
slow corrosion damage (cracking or wall thinning), is overloaded beyond its fracture
toughness.
In failure prevention, the knowledge of the maximum loading conditions which often
occur during transients is as important as the knowledge of the corrosion damage. This
is being achieved by inspections and by diagnostic monitoring of defects, pressures,
stresses, and temperatures during all types of operation and by life predicting
(32)
(33)
instrumentation such as turbine rotor stress , and boiler drum stress monitors .
For the above reasons, the priorities are:
1. All safety-related operation, layup, and testing procedures such as safety valves,
critical speeds, combustion, and water hammer.
2. Thermal and low cycle fatigue damage prevention such as control of drum, heater,
and turbine rotor and piping stresses, and boiler circulation.
2-26

3. Other operation-related problem prevention including control of boiler carryover,

condenser vacuum, deaerator water hammer and water piston, deaerator storage
tank water flashing and steam space collapse, pump cavitation (particularly for
boiler feed pumps), feedwater heater non-condensable gas removal, water level
controls, drains, and superheater and reheater overheating.
4. Water and steam chemistry control including:
x
Control of ingress, generation, transport, and deposition of impurities
Control of all types of corrosion and erosion
Control of deposits in boiler, superheater, reheater, and turbine which can lead
to corrosion, overheating, and loss of MW capacity and efficiency
Control of hideout of phosphate and other chemicals
Table 2-7 lists the items of concern that were identified in EPRI report EL-975(7). The
report summarizes a survey of the cycling capabilities of the fossil-fired generating
units in the US and Canada.
Additional concerns include increased risk of condenser leaks, increased ingress of
aerated makeup, and high air inleakage during startups.
For the cycling units, in addition to the recommended physical changes to the
conventional plant configuration, one fundamental solution to the problems of cycling
is to give closer attention to optimization of startup, shutdown and load change
sequences. Such an optimization process can be performed most readily through the
use of effective analytical tools and control/monitoring instruments designed
specifically for this purpose.
The longterm reliability and availability of cycling units rely on the operator's attention
to, and recognition of, the impact of life expenditure due to thermal cycles and other
transient conditions on plant components. Since the effect on life expended of each
cycle is small, the overall effect may not be readily apparent to plant operators during
the event and may not be recognized and properly considered in making the day-today operating decisions. Yet, the longterm cumulative effect of such cycles can result in
extended and expensive forced outages requiring major repairs or component
replacement.
2-27

Table 2-7
List of Concerns for Cycling Units
(CH indicates the items affected by water and steam chemistry)
x
x
x
x
x
x
x
x
x
x
x
x
x
x
increased boiler component cyclic stress with loss of life

increased turbine rotor cyclic stress with loss of rotor life
increased thermal stress on turbine rotor, steam chests,
valves, and inner casing leading to corrosion fatigue
increased solid particle erosion of HP and IP turbine blading
from superheater and reheater tube exfoliation
turbine vibration during startup/shutdown
possibility of furnace implosion/explosion during
startup/shutdown
steam requirements for maintaining condenser vacuum
the need for improved boiler control to minimize unit restart
and reloading times
acid dew point condensation - corrosion and plugging of
air preheaters and back end ductwork
flame scanner monitoring problems requiring much attention
burner turndown ratio/flame stability at low loads - feeder
turndown and mill response times during load ramps too slow
increased frequency of chemical cleaning and more
monitoring and control of steam and water chemistry needed
poor back end equipment performance at low load conditions
increased possibility of mill fires and explosions during
frequent starting and stopping of a unit; particularly true for the
more volatile western coal
distortion and internal rubbing of the boiler feed pump, if
pump is not fully warmed up at startup
CH
CH
CH
CH
CH
CH
By conducting appropriate training programs on operational considerations for cyclic

duty, plant operators become more aware of conditions in which thermal stresses on
plant components might be particularly excessive, and be better able to take corrective
actions to avert them. In addition, the use of effective analytical tools (such as
computer modeling to simulate plant operation under different conditions) and
(34-38)
and control of instruments/equipment (such as boiler stress
diagnostic monitoring
analyzer and turbine rotor stress indicator) can provide valuable benefits and guidance
to plant operators for reliable and efficient operation under cyclic duty.
The monitoring should include water chemistry, deposits, exfoliation, and corrosion.
2-28

2.5 EFFECTS OF STEAM CYCLE DESIGN AND OPERATION

The cycle design goals for base load, cycling and peaking operation are indicated by
the concerns listed in Table 2-7 and briefly described in this Section. Retrofits have
been developed aimed at improving water chemistry control, temperature matching,
and thermal stresses during cycling operation.
Operator actions significantly influence the cycle chemistry and cycle component
corrosion during cycling operation. The chemistry is influenced by the actions aimed at
the prevention of ingress and removal (blowdown, use of condensate polishers, fill and
drain, etc.) of impurities. Operator actions which control cycle component stresses
(temperature matching, ramping rates) also control the stress induced corrosion
mechanisms.
(8)
A 1977 EPRI workshop on cycling gathered together utilities with experience in
handling cycling problems when using formerly base-loaded fossil plants. Among the
recommendations resulting from that workshop were the following items, most of
which relate to capital expenditure items for improving cycling performance(17). The
items marked with CH indicate effects on water chemistry or corrosion.
Incorporate steam bypass systems
CH
Incorporate full arc admission
Add additional controls and monitoring equipment
CH
Incorporate variable pressure operation
CH
Use two half-sized boilers
Install turning gears on ID fans
Incorporate a condensate polishing system
Incorporate better turbine seals
Use integral separators on once-through units
Install smaller coal mills for low load operation
Install feedwater cleanup loop
CH
CH
CH
2-29

Drum Boiler vs. Once-through Boiler Units(7-12)

Generally, both types of units can be converted or originally designed for cycling
operation. The most important part of such conversion is matching the steam and
turbine metal temperatures. This is usually easier for drum boilers. In once-through
supercritical boilers, the transition through the critical region and from the evaporation
mode to the once-through mode, and carryover of chemical impurities from the flash
tank are of concern.
Sliding Pressure Operation(17,39-42)

Changing the turbine controls from partial arc admission to full arc admission and
sliding pressure operation can reduce thermal stresses and improve efficiency and
water and steam chemistry control. The advantages of sliding pressure operation are:
1. Steam temperature distributions within the turbine are more uniform. Minimum
variation of first stage shell temperature.
2. Improved overall power plant efficiency - feed pump and other auxiliaries.
3. Reduced pressure results in lower heat transfer coefficient and correspondingly
lower thermal stresses.
4. Reduced pressure - eases components' duty cycle.
5. Improved and extended control of primary and reheat steam temperature - due to
an increase in the latent heat of vaporization as pressure is decreased.
6. Improved water and steam chemistry control by reducing boiler carryover,
improving boiler circulation in the natural circulation drum boilers, and possibly
reducing scale growth in waterwall tubes at lower pressures.
Boiler Concerns(15-17,25,39,40,43-46)
Boiler consideration for cycling operation cover the areas of stress generation,
circulation in waterwall tubes, boiler water chemistry, and steam chemistry. The
problems are prevented by a combination of operator and chemist actions and boiler
design.
The major factors affecting boiler design considerations for cyclic duty are:
x
number of cycles
heating and cooling rates
2-30

x
component thickness, diameter and material
operating temperature level
waterwall tube circulation in drum boilers
Heavy thick-walled steam generator components (steam drums, superheater header

tees, valves, etc.) should be watched closely for possible failure due to excessive
thermal stress (with possible corrosion effects of water and steam chemistry). Startup
rates of boilers containing such components have been limited by simple but effective
rules governing the rate of temperature change in these components. In the past, these
limitations did not substantially restrict unit availability because such units were
operated in the base-load mode. With the conversion of such units to cycling duty,
these simple but conservative startup limitations may no longer be adequate to protect
against excessive loss-of-life.
Cyclic stresses resulting from such temperature changes must, therefore, be
reconsidered in the boiler as well as the turbine. They result from either
x
temperature differences through the thickness of a containment; or
temperature differences between components attached to each other.
The steam drum and superheater outlet headers are the two thickest parts of a boiler
and must be considered when thermally cycling the boiler.
There are two general areas in a boiler where parts with different temperature
characteristics are attached to each other. The first area covers superheater and reheater
tube legs, which penetrate the enclosure and connect to an outlet header. These legs
must have sufficient flexibility to permit one end to move with the header at final steam
temperature, and the other end to move with the enclosure wall at saturation
temperature. The flexibility can be designed into a new boiler, but it may be limiting
on an older one, particularly a wide one.
The second area is the attachment of nonpressure parts, such as windboxes and
vestibules, to tube walls that are at saturation temperature. These parts respond to air
or flue-gas temperature rather than saturation temperature, and change temperature
more slowly.
EPRI developed a boiler thermal stress and condition analyzer to evaluate the condition
of boiler components during episodes of high temperature and pressures or high
thermal stresses(33). This analyzer operates on-line to accumulate a history of damaging
incidents.
2-31

In one EPRI study of a cycling boiler (CS-2438) (44), it was found that on/off daily load
cycling of the boiler requires design changes before this type of operation is performed
on a regular basis. Even with design changes, the thermal shock of the boiler that
occurs with operation of once-through boilers when "cold" water enters a "hot" boiler
may eventually lead to failure of boiler components. Recommended design changes
included:
x
Change boiler furnace to spiral design.
Change bypass system, use full pressure separator design, or full pressure separator
recirculation pump design.
Make provision for quick water cleanup and provide for feedwater heating before
firing boiler.
Add flame monitoring system.
Provide new burners and burner control system.
Upgrade unit control system.
Add new and larger computer to better monitor temperatures in boiler and turbine.
Boiler Carryover - in drum boilers is sensitive to the drum level which could be
elevated along the whole drum length or locally during shutdowns, startups, and rapid
load or boiler pressure changes. Operating events such as the use of circulating pumps,
coal mills and burners, and soot blowing can significantly influence the drum level. It
is imperative to experimentally determine the carryover for all modes of operation and
after equipment changes are made, particularly after installation of new burners which
may change the boiler heat flux patterns.
The water chemistry parameters which can increase boiler carryover during cycling
operation and startups include: high dissolved and suspended solids and high
hydroxide alkalinity, particularly when combined with organic matter.
Exfoliation - of oxides (mostly magnetite) from superheater, reheater, and steam piping
can be accelerated by more frequent shutdowns. The exfoliation occurs during
shutdown because the ID of the tubes and piping cools faster than the metal, and
because of the difference in the coefficient of thermal expansion between the oxides and
the steel(47). The exfoliated oxides collect in the lower bends of the SH and RH pendant
platens and, during the following startup, are carried into the turbine causing solid
particle erosion(48). These oxides also increase the iron and copper concentration in
condensate and feedwater and cause overloading of condensate polishers. The oxides
extracted through turbine extractions go through feedwater heaters and heater drains
2-32

into the suction of the boiler feed pump and then back into the boiler, and thus bypass
the condensate polishers.
Mud Drums - or lower headers often collect large quantities of oxides (up to hundreds
of pounds) in the form of sludge. The quantity of sludge can be reduced markedly by
blowing down the lower boiler drains just prior to shutdown at 50 to 70 psi (0.3-0.5
MPa), by drain and fill, by manual cleaning during shutdown, and by blowing the
lower drains during the early startup. During startups, circulation from the mud
drums through the economizer into the boiler transports large quantities of iron and
copper(28).
Turbine(18,42,49,50)
Cycling and peaking operation can affect the turbine by generation of corrosive
deposits which reduce generating capacity and efficiency, by producing high thermal
and vibratory stresses, by introduction of exfoliated oxides from the superheater and
reheater (leading to solid particle erosion), and by introducing humid air which can,
together with corrosive deposits, lead to pitting during layup. A positive effect of
cycling can be washing of the accumulated deposits during startup.
Some of the possible turbine modifications that have been considered for cycling duty
include:
x
layup dehumidification or nitrogen blanketing to reduce corrosion
change from constant to sliding pressure(40-42)
change from partial arc to full arc admission(49)
turbine by-pass(49-50)
design changes to decrease thermal strains (decreasing notch effects, better heating
(50)
and cooling)
materials with higher ductility
changing water glands to steam glands
bearing and turning gear modifications
instrumentation and control
2-33

The implementation of any or some of these modifications or processes is clearly a

function of the benefit-cost ratio, which includes the cost of generation for that
particular plant.
Life Expenditure(50) - Cycling duty, which can range from daily load changes to daily
startup and shutdown, imposes a much more severe duty on a turbine-generator than
base load operation does. Inherent with cycling are large and frequent changes in
temperature (see Figure 2-13) which accelerate the expenditure of component life.
Once the component life is expended, cracks will be initiated, and (depending on
material properties, operating stress levels and stress concentration, the severity of the
transient condition and corrosiveness of steam and deposits) the cracks may propagate
rapidly. If the resulting crack is not detected early, propagation can progress to a point
where a permanent repair cannot be made and the component must be replaced.
Figure 2-13 Calculated and measured HP rotor temperatures - startup
The cycling duty will also affect the unit's alignment, clearances, etc. There are,
however, methods to reduce the magnitude of these temperature changes in the turbine
and also to make modifications which will better enable the unit to accommodate the
detrimental effects of cycling duty.
2-34

Turbine related limitations during rapid load changes, shutdowns, and startups
include:
x
thermal stress
differential expansion
rotor and blade vibration
stress and strain cycling of the highly stressed areas due to startups (LP blade
attachments, shrunk on disks), i.e., low cycle fatigue
The critical turbine limitation during cyclic duty are the transient thermal stresses in
the large high temperature components, particularly the rotor, HP and IP inner
cylinders, during heating and cooling. Cyclic thermal stresses are especially
accentuated during periods of rapidly increasing load, as in the case of two-shift
cycling where the unit has to be brought quickly on-line. These thermal stresses have
the potential for causing high rotor bore stresses or local surface yielding which can, if
severe enough, result in premature initiation of surface cracks.
Thermal stresses in the turbine arise, in part, because of an inherent difference in the
rate of temperature change, with respect to time, between the boiler and the turbine.
For example, after shutdown of a unit, the boiler cools at a faster rate than the turbine.
As a result of this, the subsequent restart of the unit is characterized initially by a steam
temperature which is below the turbine metal temperature. At a later time in the
startup sequence, steam temperature has a tendency to become excessively high as
compared to turbine metal temperature. This mismatching of steam temperature and
turbine metal temperature is the driving potential for thermal stresses in the turbine.
The magnitude of thermal stress depends on the total required temperature change and
on the temperature ramp rate. Thermal stress is, therefore, the most important factor in
establishing the rate at which turbine operating loads can be varied. Turbine fatigue
index showing the number of startup cycles for initiation of fatigue cracks for different
rates of first stage temperature change is shown in Figure 2-14. On-line thermal stress
analyzers have been developed for turbines which monitor the behavior of the turbine
during startup or load change. Any adverse condition which results in loss-of-life of
the rotor forgings is tracked, and episodes are accumulated to give an estimate of cyclic
life expenditure and the remaining rotor life. An important benefit of continuous stress
evaluation is that it offers guidance to plant operators during transient cycling
operations. By monitoring calculated stresses, operators can make more efficient use of
the equipment and thus better satisfy the plant cycling requirements. For the particular
type of transient operation, it is necessary to select a cyclic life expenditure target value.
This selected value then establishes the allowable thermal surface stress limit which
governs the turbine loading rate.
2-35

As already discussed, sliding pressure operation improves many operating problems,

including thermal stresses in the heavy sections of turbines. The change of turbine
valve operation from partial arc admission to full arc has similar beneficial effects (49,50).
These two modes of operation are illustrated in Figure 2-15. Rotor thermal stress as a
function of time is for the constant pressure, partial arc and sliding pressure, full arc
operation shown in Figure 2-16(49). The full arc operation can extend the rotor life from
1,000 to over 100,000 cycles.
In combination with corrosive impurities, the stresses resulting from the above
situations can lead to stress corrosion and corrosion fatigue cracking. In the high
temperature turbine sections, sodium hydroxide is the only active corrosive chemical.
Salts and acids either evaporate or are dry (non-corrosive). Many corrosive substances
are active in the LP turbine.(65)
In units which synchronize at very low loads, the following problems can be
encountered:
x
shift of the corrosive salt zone to the highly stressed L-0 blades
reversed circulation of steam at the LP exhaust (windage) leading to high vibratory

stresses and water droplet erosion of the L-0 and L-1 trailing edges
C
316
First Stage Temperature Change (F)

600
1000 cycles
2000 cycles
3000 cycles
5000 cycles
10,000 cycles
20,000 cycles
500
400
260
204
300
149
200
93
100
38
0
0
20
40
60
80
Time to Change Load/Throttle Conditions (minutes)
100
Figure 2-14 Turbine fatigue index vs. temperature change and time(51)
2-36
0
120

Partial Arc Admission
Full Arc Admission
From boiler
From boiler
Stop valve
Stop valve
Stop valve
with internal
by-pass
Stop valve
Open
Closed
Control
valves
(all open)
Control valves
Open
Closed
HP turbine
HP turbine
Figure 2-15 Turbine valves for partial arc and full arc admission
Compressive
Stress, KSI
30
Partial arc
20
10
Full arc
>100,000
Tensile
Stress, KSI
0
10
Cyclic life 10,000
20
30
0
10
20
30
40
Time, minutes
50
60
70
Figure 2-16 Rotor thermal stress as a function of time with sliding pressure.
Initial throttle to metal temperature difference = +50F, throttle temperature ramp =
200F/h, loading rate = 2% per minute
2-37

Turbine Bypass Systems(43,49.50)

Large external turbine bypass systems (see Figure 2-17) enhance the startup flexibility
and load changing capability of the unit by better control of thermal stresses and the
impurities carried into the turbine with the steam. With turbine bypass systems, units
can be made equally suitable for peaking and base-load duties. Full capacity turbine
bypass systems permit rapid reloading of the unit even after full load rejection or
continuous operation at auxiliary house load. European utilities have been using large
external turbine bypass systems for over 30 years and in recent years European designs
have been trending toward full 100% external turbine bypass systems.
Large external 100% bypass systems allow the full boiler flow at any load to be
transferred from the turbine to the bypass system and vice versa without any major
pressure changes. In addition, with a 100% bypass, large volumetric flows at low
pressures can be established during startup, thus guaranteeing a high steam velocity in
the superheat and reheat boiler sections.
Turbine bypass systems offer improvement that can be summarized as follows:
1. Starting and Loading Characteristics - Steam flow in the reheater is established at an
early time in the startup. Therefore, control of the firing rate is limited by the
allowable rate of drum heating, not by concern for protecting the reheater. In this
way the overall startup time can be reduced.
2. Independent Boiler/Turbine Operation - Steam is not admitted from the boiler to
the turbine during startup while the steam temperature is excessively lower than the
turbine metal temperature. This can minimize the temperature mismatch which
plays an important factor in cyclic life expenditure of major turbine components.
3. Decreased Solid Particle Erosion - During startup, exfoliated oxides (magnetite)
carried over from the superheater, reheater, and steam pipes present an erosive
problem to the turbine and valves.
4. Prevention of turbine contamination by corrosive impurities.
5. Reduction of accumulation of HP turbine deposits of copper and phosphate which
can cause reduction of the MW generating capacity and efficiency.
2-38

Ventilator
valve
Reverse
flow valve
Steam
from boiler
superheater
Intercept
valve
Condenser
Reheater
Control
valve
H.P.
turbine
R.H.
turbine
L.P
bypass
valve
H.P.
bypass
valve
H.P. bypass
water coltrol
valve
Generator
Condenser
L.P. bypass
water control
valve
Figure 2-17 Turbine bypass system
Feedwater System Cleanup Loops(14,45,46,52,53,54)

Cycling units should have an auxiliary sub-loop between the condenser and the outlet
of the heaters to facilitate the cleanup of the preboiler cycle (Figure 2-18). The purpose
of the cleanup loop is to remove the metal oxides, which enter the feedwater from the
surfaces of feedwater heaters, and the oxides which deposit on feedwater surfaces due
to the changes of pH and temperature which occur during system layup, fill, and
startup. The principal items for the successful operation of the cleanup loop are: a) a
low-pressure cycle line, and b) a condensate polisher or filter to process at least 25% of
the rated flow. Following an outage, the condensate must be properly treated and
recirculated through the preboiler cycle to permit deaeration and removal of suspended
solids. Recirculation, when performed at sufficiently high velocity, removes
contaminants from preboiler surfaces.
Based on experience with cleanup systems, a velocity of 0.6 m/s (2 fps) (approximately
25% of the maximum continuous rating, MCR), is recommended for the current designs
of feedwater heaters. Recommended procedures incorporating the bypass system,
(54)
condensate polishing, and deaeration for cyclic units have been discussed . Cleanup
time after long shutdowns (greater than 4 days) requires about 8 hours to reduce
impurities in the feedwater to levels suitable for use in boilers. Units started up after
outages of less than 4 days generally require 3-4 hours to clean up the feedwater. No
preboiler cleanup is required after a hot restart if the condensate quality meets specified
limits.
2-39

Condensate Filtering and Polishing(15,45,54,67)

Removal of corrosion products (iron and copper oxides) and other impurities from
feedwater during the cleanup operation of cyclic units is one of the best water
chemistry control measures. It can be achieved with deep-bed demineralizers,
powdered-resin demineralizers, magnetic or other filters. With proper flow and
deaeration, it is possible to remove 85-95% of the suspended contaminants with a
mixed-bed condensate demineralizer. Optimum filtration efficiency during startup is
2
achieved when the flow rates are greater than 0.02 m/s (25 gpm/ft ) of resin area for
deep-bed demineralizers. Contaminant breakthrough can occur rapidly during
cleanup if suspended solids levels are high. Protection against this condition is
possible by limiting the demineralizer runs (to 24 hours or less as required) or to a
differential pressure of 345 kPa (50 psig).
Powdered-resin demineralizer filtration efficiency equals that of a deep-bed system.
Design flow rates for these units are approximately 0.3 cm/s (4 gpm/ft2) of resin area.
While these units may have less total ion exchange capacity than deep mixed-bed units,
they are relatively free of incidents of "crud throw" or the release of filtered metal oxide
particulates reported with deep mixed-bed units. This is an important consideration in
startup/cleanup for a cyclic unit.
Condensate polishers also remove undesirable cations and anions such as sodium,
chloride, sulfate, organic acid anions, and carbonate. These impurities are at higher
concentrations during startups, and their concentration is also influenced by load
changes during cycling. Carbonate formed from CO2 entering with air inleakage can
act as an eluent and replace the already exchanged anions from the polisher resin.
Air Inleakage and Deaeration(15,45,53-61)

During layup, startup, and cycling, large quantities of air can be introduced by:
x
system filling with aerated water from storage tanks,
air saturation of water in condenser and deaerator storage tank, and
increased air inleakage because a larger portion of the cycle is under vacuum.
While both tray and spray deaerators perform well at all loads (see Figure 2-19),
condensers do not deaerate well until 30-50% of the thermal load is reached (see Figure
2-20)(62). Condenser deaeration can be improved by increasing the deaerating capacity
and by retrofitting steam blanketing and other means(9,57-61) such as ensuring that the
makeup water is introduced above the tubesheet.
2-41

Air infiltration in cycling units can result from design and operation as follows (55):
(a) Some system designs include heater drip pumps which return drips to the
condensate or feedwater. At low loads, oxygen contents as high as 500 ppb in the
drips have been noted.
(b) Reduction of a system load to below 60% of capacity generally results in a reduction
of one or two of the low pressure heaters from a positive pressure to below
atmospheric pressure. Leakage of air through the various seals results in oxygen
contamination of the steam condensing on the tube bundles.
(c) Addition of undeaerated makeup water directly to the condensate or feedwater
causes extra oxygen introduction to the cycle. In base-load systems, contamination
from makeup sources such as storage tanks is less important since little water is
transferred to and from surge tanks. In peaking units, it can be significant since
there is considerably more shrinkage and expansion occurring in condensate surge
tanks due to frequent load changes. When undeaerated makeup or surge water is
introduced, portions of the preboiler system will become contaminated with air
unless it is introduced into the deaerating section of the condenser or to a deaerator.
If the makeup and surge water storage reservoirs are not resistant to oxygen attack
nor protectively lined, corrosion products may also be introduced.
(d) Reduced air removal efficiency of deaerating equipment can be caused by cycling
operation. Systems that are shut down and started frequently, such as in twoshifting and peaking operation, are subject to significant corrosion problems if a
proper design to exclude air infiltration is not used by the plant designer. In this
mode, it is possible to add more oxygen into the cycle than in several months of
normal base load operation. Cyclic units that may be idle overnight or on weekends
should include the following operating and design features:
Maintain condenser vacuum and turbine seals during brief shutdowns. This
will protect both low- and high-pressure condensate systems from oxygen.
Turbine water glands are not effective seals at low load. Use steam seals.
Provide auxiliary steam to pressurize the deaerator and keep deaerator

pressurized during short outages. If auxiliary steam is not available, pegging
steam from an adjacent boiler or the drum should be used. For longer outages,
nitrogen blanketing may be more convenient.
Blanket the boiler with nitrogen or steam under pressure. The nitrogen or
steam-injection systems should be automatic with multiple points of addition on
boiler, deaerator, superheaters, and feedtrain vents. While a unit that is baseloaded may be able to function with manual systems for introducing nitrogen
2-42

and layup chemicals, a unit with frequent shutdowns requires a rapidly

responding automatic system to ensure the introduction of steam or nitrogen.
The effect of turbine steam seals and nitrogen blanketing on iron concentration during
a cold startup is illustrated in Figure 2-21.
% Loading
120
d oxygen
110
dissolve
100
xpected
90
Normal e
80
70
Guaranteed dissolved oxygen
60
50
40
30
20
10
Tray
Spray
0
0
0.001
0.002
0.003
0.004
0.005
0.006
Dissolved Oxygen in Effluent (ml/l)
0.007
0.008
Figure 2-19 Expected dissolved oxygen at the deaerator outlet vs. load for tray
and spray deaerators
2-43

Dissolved Oxygen (ppb)
40
30
Without auxilliary deaerating device
20
With jet deaerating device
10
With bubbling device
0
0
20
40
60
80
Heat Load (%)

Source: F.J. Pocock, Prepared Discussion to J. Brown and R.E. Massey, "Condensate, Feedwater, Steam
Sampling and Analysis in Ontario Hydro Thermal Generating Stations. "Proceedings of the 41st
International Water Conference, October, 1980
Figure 2-20 Condenser deaerating capacity with and without retrofitted devices(62)
2-44
100

Condenser Cleanup - There is often an accumulation of corrosion products on the

bottom of the hotwell and even on condenser tubes. The hotwell corrosion products
should be cleaned during shutdown, and the hotwell water can be cleaned prior to a
startup by bypass filtration or circulation through condensate polishers. The tube
bundle and the condenser structure and walls can be cleaned by washing with the
turbine hood sprays prior to a startup.
Use of these procedures will ensure feedwater that is low in iron, copper and silica
contamination.
HP
turbine
LP
turbine
IP
turbine
Condenser
Hotwell
Boiler
Recirculation valve
Dearator
Polisher
HP heaters
Cleanup loops
LP heaters
Drip pump
Source: B.T. Hagewood, H.A. Klein, and D.E. Voyles, "The Control of Internal
Corrosion in High-Pressure Peaking Unit," Proceedings of the American Power
Conference, Vol. 30, Chicago, Ill., 1984.
Figure 2-18 Condensate/feedwater cleanup loops(46)
2-40

Iron (ppb Fe)
25,000
20,000
Without turbine
steam seal and
nitrogen blanket
15,000
10,000
5,000
With turbine
steam seal
and nitrogen
blanket
0
Hotwell
Condensate Economizer
booster pump
inlet
discharge
Cyclone
outlet
Primary
furnace
outlet
Secondary
superheater
outlet
Source: F.J. Pocock, Prepared Discussion to J. Brown and R.E. Massey, "Condensate, Feedwater, Steam
Sampling and Analysis in Ontario Hydro Thermal Generating Stations. "Proceedings of the 41st
International Water Conference, October, 1980
Figure 2-21 Cycle iron concentration during a cold startup for two layup
practices(62)
With the use of pegging steam, the oxygen content of the feedwater can be reduced to
below 10 ppb during startup. Pressurization of the system in a banked condition will
prevent oxygen infiltration in the deaerator storage water. Pegging steam must be
provided to maintain a pressure of 69-103 kPa (10-15 psig) until the turbine extraction
steam is available to the deaerators(59,60). If the supply of steam is inadequate to heat all
the incoming feedwater to a temperature above 100C (212F), air will be aspirated into
the deaerator and contaminate the incoming feedwater with oxygen. It is important
that either steam or nitrogen pressure be maintained on the deaerator during outages.
If the water in the deaerator storage tank becomes aerated, the elimination of oxygen
cannot be accomplished during startup unless there is a facility for recirculation.
In systems not having a deaerating heater, it is impractical to pressurize or exclude
oxygen from the feedwater cycle when the unit is out of service. In such systems,
deaeration is achieved solely in the condenser. In order for the condenser to deaerate, a
vacuum must be maintained in it. This is seldom practical during an extended outage.
A more reasonable approach is to recycle and deaerate the condensate in the system
prior to startup. This requires a recycle line to be connected from the discharge of the
feedwater heaters back to the deaerating section of the condenser. This will prevent the
2-45

air-rich feedwater in the preboiler system from being introduced into the boiler. The
turbine must be sealed and condenser vacuum established prior to recycle. To establish
vacuum and ensure a more rapid exclusion of noncondensible gases, the condensate
should be heated to about 79C (175F) at the outlet of the heaters, during recycle. This
can be accomplished by injecting steam into the steam side of one of the feedwater
heaters.
Makeup Addition - Addition of undeaerated makeup water to the condensate
significantly upsets the oxygen control (see Figure 2-22) and increases corrosion
potential in the preboiler cycle. Makeup water should be atomized and treated by
steam in the upper part of the condenser tube bundle to provide effective deaeration.
Condensate Oxygen Concentration (ppb)
120
100
1% makeup rate
(% of main steam flow)
80
0.7%
60
0.5%
40
0.3%
20
0
6
10
11
12
Saturated Oxygen Cencentration (mg/l)

58
38
32
27
21
16
113
100
90
80
70
60
Makeup Water Temperature (F)
10
50
7
45
Source: Y.H. Lee and D.M. Sopocy, "Cost Benefit Analysis of Backfiting Makeup Degasifiers,"
Materials Performance, Vol. 24, No. 3, May 1985
Figure 2-22 Effect of air-saturated makeup water on condensate oxygen level(59)
2-46

At startup, or at low loads, the heater drips may contain as much as 500 ppb of oxygen
and, therefore, they should be introduced into the condenser through atomizing
devices. Drains at temperatures below saturated steam temperature should be
introduced above the tube bundle; drains with temperatures above saturated steam
temperature should be introduced between the tube bundle and the hot well.
Condenser Deaeration
Efficient air removal is essential for achieving good condenser deaeration at all loads.
Most condensers provide adequate deaeration at high loads; however, at low loads or
on startup of peaking or two-shifting units, the deaeration is marginal (see Figure 2-20).
It can be improved by retrofitting steam sparging and other means.
The prime factors affecting condenser deaeration at low loads are the temperature rise
of the circulating water, air inleakage, and deaerating capacity of the vacuum pumps or
air ejectors. At low loads, the temperature rise of the cooling water across the
condenser tubes is less than at full load. This results in a reduced condenser pressure
and corresponding saturated steam temperature causing a reduction in mass-steam
condensation area and an increase in the air cooler area. Under these conditions, an
increased oxygen concentration is caused by subcooling. Since air ejector capacity is
constant, and normally designed for full-load operation, more wet steam and less gas is
ejected. The remainder of the gas accumulates within the condenser shell, increasing
the partial pressure of the gas throughout the bundle.
Tests have been run which indicate that air inleakage at 25% load can be double that at
full load. At low loads, or startup, it is necessary to remove the air to ensure a
condenser vacuum. Air ejector overloads lead to increased condenser pressure and
dissolved oxygen content, which in turn promotes corrosion in the cycle. This
condition and that due to insufficient sweeping of air deep in the tube bundle, can be
obviated by using an additional vacuum pump or ejector. With proper design, 12.7
mm (0.5 in.) or as low as 6.35 mm (0.25 in.) Hg, absolute suction pressure can be
attained.
2.6 ALTERNATIVE WATER TREATMENT CHEMICALS(3,63,64)

During the past 15 years, many new amine, oxygen scavengers, and polymeric
dispersants have been introduced. These chemicals are mostly used in industrial steam
cycles and their use in high pressure utility units is controversial. All types of utility
units can be operated with the water treatments and chemicals recommended in EPRI
guidelines. The main concern with the use of the alternative organic water treatment
chemicals is their thermal decomposition (breakdown) and production of organic acids
and carbon dioxide.
2-47

Before applying these new chemicals, their properties should be carefully determined
and experience with each should be verified. Then, within a few weeks of the first
application of the new chemical, the cycle chemistry should be analyzed in much more
detail than during the normal operation and any breakdown products should be
identified(3).
The selected treatment should protect all cycle components and prevent generation of
corrosion products, and general and localized corrosion. These chemicals and their
breakdown products should be compatible with all cycle component materials and the
layup practices, and with all environmental and health regulations. Decomposition of
organic compounds at the elevated and high temperatures in feedwater and boilers can
lead to increased feedwater and steam cation conductivity and reduced pH. Most of
the applications are for low- and medium-pressure industrial units, but some of these
chemicals are also being used in utility cycles. The use of some of these products can
lead to corrosion, buildup of deposits, and other problems. It should be kept in mind
that the overall philosophy of the EPRI fossil plant cycle chemistry program is to keep
the cycle as pure as possible with as few chemical additions as possible.
The alternative water treatment chemicals (all organic) fall into the following
categories:
x
neutralizing and filming amines for feedwater, steam, and condensate
reducing agents (oxygen scavengers)
dispersants and chelating agents for prevention of boiler scale and removal of
hardness and corrosion products (these should only be considered and used in low
pressure (<1000 psi, 7MPa) units)
There are hundreds of formulations of the above chemicals and their mixtures.
To evaluate the effects of any water treatment chemical, data pertinent to its chemical
transport, decomposition temperature and products, cycle material corrosion, deposit
and scale buildup, and analytical interferences should be known. These needed data
include:
x
hydrothermal stability in the cycle
kinetics of reactions
decomposition products and their effects
analytical interferences
2-48

x
how to monitor/analyze
toxicity of the product, decomposition products, deposits, etc.
measured effects on pH, specific conductivity, cation conductivity, iron, and copper
concentrations in the feedwater, boiler water and steam
stability in chemical addition tanks and storage containers
solubility and volatility of the chemical and its decomposition products
behavior of dried-out solutions (deposits in reheaters, superheaters, turbines, valve

gluing)
behavior under short- and long-term layup conditions and during startup
(decomposition - acid formation, scale formation, disposal, etc.)
The utility users of water treatment chemicals need to know the pressure and
temperature range of their application and the nature and behavior of the
decomposition products. These are not usually supplied by the chemical
manufacturers, and a utility will need to perform comprehensive monitoring before
considering their application(3).
2.7 REFERENCES AND BIBLIOGRAPHY FOR SECTION 2

1. Interim Consensus Guidelines on Fossil Plant Cycle Chemistry. EPRI CS-4629,
RP2712-1, June 1986.
2. Guidelines on Cycle Chemistry for Fluidized-Bed Combustion Plants. EPRI TR102976, September 1993.
3. Selection and Optimization of Boiler Water and Feedwater Treatments for Fossil
Plants. EPRI TR-105040, March 1997.
4. Cycle Chemistry Corrosion and Deposition: Correction, Prevention, and Control.
EPRI TR-103038, December 1993.
5. Transport of Chemicals in the Steam Cycle. In Ref. 15.
6. O. Jonas. Transport of Chemicals in the Steam Cycle. Paper No. 245,
Corrosion/85, NACE, March 25, 1985, Boston.
7. Survey of Cyclic Load Capabilities of Fossil-Steam Generating Units, EPRI EL-975,
Final Report, February 1979.
2-49

8. Cycling Ability to Large Generating Units Workshop, EPRI WS-77-50, November

1977.
9. Proceedings: 1983 Fossil Plant Cycling Workshop. EPRI Report CS-3979, April
1985.
10. Proceedings: 1985 Fossil Plant Cycling Workshop. EPRI Report CS-4723,
September, 1986.
11. Proceedings: 1987 Conference of Fossil Plant Cycling, EPRI Report CS-6048,
December, 1988.
12. Fossil Plant Cycling. EPRI Conference, Washington, D.C., December 4-7, 1990.
13. Cycling of High-Pressure Steam Power-Generating Units with Drum Boilers. EPRI
CS-2340, Final Report, April 1982.
14. Improvement of Chemistry Control During Startup of Fossil Units. ASME
Workshop, St. Louis, MO, April 9-10, 1997.
15. The ASME Handbook on Water Technology for Thermal Power Systems. Paul
Cohen, Editor-in-Chief. EPRI Research Project RP-1958-1, ASME, 1989.
16. Combustion - Fossil Power Systems, Combustion Engineering, Inc. 1981.
17. A. F. Armor and F. K. L. Wong. Fossil Plant Cycling Program. In Ref. 9.
18. O. Jonas. Understanding Steam Turbine Corrosion, Paper No. 55, Corrosion/84,
NACE April 2-6, 1984, New Orleans.
Also: Steam Turbine Corrosion, Materials Performance, 24, 2, February 1985, pp.
9-18.
19. R. Garnsey, Combustion, Vol. 52, No. 2, p. 39, 1980.
20. G. M. W. Mann. The Oxidation of Iron Base Alloys Containing Less Than 12% Cr
in High Temperature Aqueous Solutions. in High Temperature, High Pressure
Electrochemistry in Aqueous Solutions, NACE, Houston, Texas, 1976. pp. 34-47.
21. G. M. W. Mann. History and Causes of On-Load Waterside Corrosion. Br.
Corrosion J. 12 (no. 1, January 1977): pp. 6-14.
22. State-of-Knowledge of Copper in Fossil Plant Cycles. EPRI TR-108460, September
1997.
23. Metals Handbook, Volume 19 - Fatigue and Fracture, ASM International 1986.
2-50

24. Metals Handbook, Volume 13 - Corrosion, ASM International 1987.

25. B. Dooley and W. McNaughton. Boiler Tube Failures: Theory and Practice. EPRI
Book, TR-105261, 1996.
26. D. D. Macdonald and G. A. Cragnolino. Corrosion of Steam Cycle Materials. In
Ref. 15.
27. J. Mathews. The Importance of Startup Chemistry to the Long-term Reliability of
Power Generating Equipment. In Ref. 14.
28. O. Jonas, et al. Copper Deposition and MW Loss Problem Solutions. Paper
presented at the International Water Conference, Pittsburgh, October 1996.
29. Corrosion Product Transport in a Cycling Fossil Plant. EPRI Report CS-5033,
February, 1987.
30. Cycle Chemistry Guidelines for Fossil Plants: Oxygenated Treatment. EPRI TR102285, December 1994.
31. Cycle Chemistry Guidelines for Fossil Plants: All-Volatile Treatment. EPRI TR105041, April 1996.
32. Monitoring & Diagnostic Center: An Overview of Operating Activities. EPRI GS7407, July 1991, pp. 4-22 to 4-38.
33. Boiler Stress and Condition Analyzer. EPRI, RN6315B(1), August 1986.
34. G. Touchton, et al. Predictive Maintenance for the '90s: EPRI Keynote. EPRI
Fourth Incipient Failure Detection Conference, Philadelphia, PA, October, 1990.
35. A. F. Armor. On-Line Diagnostics for Fossil Power Plants: The Promise and the
Reality. EPRI Workshop on Incipient Failure Detection for Fossil Plants, Hartford,
CT, August 1982.
36. O. Jonas. Incipient Failure Detection and Predictive Maintenance. Power,
January 1992, p. 61.
37. O. Jonas. On-Line Diagnosis of Turbine Deposits and First Condensate.
Pittsburgh, PA, Oct. 31-Nov. 1-2, 1994.
38. O. Jonas. Monitoring of Superheater and Reheater Exfoliation and Steam Blow.
56th International Water Conference, Pittsburgh, October 1995.
2-51

39. B. E. Laney, et al. Supercritical Unit Boiler Circuitry and Control System
Modifications for Improved Unit Turndown Capability. In Ref. 9.
40. W. P. Gorzegno. Retrofitting High Efficiency Steam Generators for Cycling
Service. In Ref. 9.
41. I. Martinez, et al. Supercritical Steam Generator Designs for Sliding Pressure
Operation. American Power Conference, Chicago, 1981.
42. H. Termuehlen. Variable-Pressure Operation and External Turbine Bypass
Systems to Improve Power Plant Cycling Performance. ASME paper 79-JPGCPwr-9, Joint Power Generation Conference, Charlotte, NC, Oct. 1979.
43. G. P. Schatzmann. Economic Peak-load Coverage by Retrofitting Existing Power
Plants. In Ref. 9.
44. Study of Universal Pressure Boiler for Cycling Operations. EPRI CS-2348, June
1982.
45. F. Gabrielli, et al. Water Chemistry Aspects of Cyclic Operation for Older High
Pressure Drum-Type Boilers. In Ref. 9.
46. B. T. Hagewood, et al. The Control of Internal Corrosion in High Pressure Peaking
Unit. Proceedings of the American Power Conference, Vol. 30, Chicago, IL, 1984.
47. The Spalling of Steam-Grown Oxide from Superheater and Reheater Tube Steels.
EPRI FP-686, February 1979.
48. Solid Particle Erosion Technology Assessment. EPRI TR-103552, December 1993.
49. D. D. Rosard and W. G. Steltz. Assessment of Fossil Steam Bypass Systems. In
Ref. 9.
50. C. R. Ernest and W. G. Gorman. Upgrading Steam Turbine-Generators for Cycling
Operation. In Ref. 9.
51. J. Bellows. Startup Procedures and Limits: A Manufacturer's Perspective. In Ref.
14.
52. R. L. Coit. Balance of Plant Options for Cyclic Duty Operation. In Ref. 9.
53. W. A. Micek and K. L. Atwood. Design Factors in Water Chemistry Control for
Boilers in Cyclic Service. Proceedings of the American Power Conference 41, 1979,
pp. 905-911.
2-52

54. F. Gabrielli, and W. R. Sylvester. Water Treatment Practices for Cyclic Operation
of Utility Boilers. International Water Conference, Pittsburgh, PA, October 31November 2, 1978.
55. H. Grabowski. Management of Cycle Chemistry. In Ref. 15.
56. O. Jonas. Deaerators, An Overview of Design, Operation, Experience, and R & D.
Proceedings of the Amer. Power Conference, Vol. 49, p. 979, 111. Institute of
Technology, 1987.
57. W. Pearl, et al. Deoxygenation in Cycling Fossil Plants. 1990 Conference on
Fossil Plant Cycling, Washington, DC, December, 1990.
58. O. Jonas. Controlling Oxygen in Steam Generating Systems. Power, May 1990.
59. Y. H. Lee and D. M. Sopocy. Cost Benefit Analysis of Backfitting Makeup
Degasifiers. Materials Performance, Vol. 24, No. 3, May 1985.
60. I. Oliker. Deaeration. In Ref. 15.
61. R. Coit. Condensers. In Ref. 15.
62. F. J. Pocock, prepared discussion of the paper: J. Brown and R. E. Massey.
Condensate, Feedwater, Steam Sampling and Analysis in Ontario Hydro Thermal
Generating Stations. Proceedings of 41st International Water Conference, October,
1980.
63. Use of Organic Water Treatment Chemicals. VGB Conference, Organische
Konditionierungs-und Sauerstoffbindemittel, Lahnstein, Germany, March 1994.
64. O. Jonas. Beware of Organic Impurities in Steam Power Systems. Power, 126, 9,
pp. 103-107, September 1982.
65. T. McCloskey, B. Dooley and W. McNaughton. Steam Path Failures: Theory and
Practice. Two Volume EPRI Book TR-108943.
66. R.B. Dooley, J. Mathews, R. Pate and J. Taylor, Optimum Chemistry for AllFerrous Feedwater Systems: Why Use an Oxygen Scavenger?. Proceedings: 55th
International Water Conference. Engineers Society of Western Pennsylvania. 1994.
67. Condensate Polishing Guidelines. TR-104422. Palo Alto, Calif.: Electric Power
Research Institute, September 1996.
2-53

2-54
3
GENERAL ASPECTS COMMON TO MOST UNITS
3.1 DEFINITIONS
Cycling
Cycling is a load following operation. The unit load fluctuates with system demand,
with the unit synchronized at very low loads during low-demand periods. A typical
load variation for cycling units might range from 30% to 100% of design capacity.
Peaking is a form of cycling in which the unit is operated only during peak power
demand periods. At off-peak hours the unit is on hot or cold standby, depending upon
the estimated time between restarts. Two-shift operation is typical of peaking units,
which generally furnish power for the morning and evening high demand hours.
Duration of Shutdown
The duration and description of shutdown periods have different definitions within the
various utility systems. For the purposes of this Guideline document, shutdown
periods are defined as follows:
x
Short-Term Shutdown (Wet)
Overnight to through-a-weekend. This might be typical of cycling-type operation. The

chemistry conditions for boiler water and pre-boiler systems are usually kept in the
normal operating range. The boiler should be full and under pressure.
x
Intermediate Shutdown (Wet and Dry)
This condition applies for periods extending more than a weekend and up to one week.
It could typify a shutdown for equipment repair of modest complexity.
Under wet conditions the chemistry is maintained in the normal operating range and
the boiler is allowed to cool. Positive nitrogen pressure is applied and maintained to
prevent air-ingress as pressure decays below positive pressure.
3-1

General Aspects Common to Most Units
Under dry conditions (needed for such operations as boiler tube repair) the boiler and
associated systems are drained hot and purged with nitrogen to remove all traces of
moisture. Air-ingress is controlled by maintaining a positive nitrogen blanket on the
boiler, superheater, and associated steam spaces until moisture is removed and the
metal cools.
For safety reasons nitrogen must be purged from all areas being serviced before
personnel ingress for repairs.
x
Longterm Shutdown (Wet and Dry)
This condition applies when the unit is out-of-service for more than one week. This
could include major equipment repair, planned outage, or a unit mothballing scenario.
Under wet conditions, hydrazine concentrations are elevated, pH is maintained above 9
(25C, 77F) and a positive nitrogen pressure is maintained to exclude air from unflooded spaces.
Under dry conditions, the hot boiler is drained and purged of all moisture with
nitrogen. A positive pressure of nitrogen is maintained in the boiler and associated
steam spaces until the boiler cools. Nitrogen blankets may be maintained for extended
periods. Alternatively the unit may be stored indefinitely under properly controlled
dry dehumidified conditions.
x
Peaking
If the unit is utilized for peaking service, the applicable hot-standby or short-term
layup condition with properly controlled chemistry should be utilized.
Again, the length of shutdown plays a major role in the type of layup procedure
selected (See Layup Section 4). The rapidity with which units can be returned to
service may place constraints on how the unit is shut down or the procedures used for
layup.
Forced Shutdown
There are several types of situations which would demand an emergency shutdown.
Each situation may affect the type of chemistry treatment which can be provided and
the method of layup(1a):
3-2

System Failure but no Equipment Failure

A system failure may be caused by a fault on the system over which the utility has little
control, such as a system blackout or loss of a critical transmission line. This would
result in rapid shutdown without the possibility of close chemical control. Most layups
under these conditions would be short-term.
Major Equipment Failure
A major equipment failure might include boiler tube failures, turbine vibration, boiler
feed pump malfunction, etc. This type of failure would normally result in rapid
shutdown without the possibility of close chemical control. Layup would probably be
longterm.
3.2 USE OF POLISHERS AND CONDENSATE FILTRATION

Condensate Polishing and/or Filtration(1b)
Condensate polishing and/or filtration is a definite asset for all operating units, and
particularly those in cycling operation. These options materially reduce startup times
and prevent high concentrations of corrosion products from entering the boiler. A
complete discussion of the benefits of condensate polishing can be found in the EPRI
Condensate Polishing Guidelines(2).
Clean-up loops (Figure 2-18) that include either or both condensate polishing and
filtration provide for rapid cleanup of the pre-boiler system and will reduce startup
time by removing corrosion products and other contaminants such as silica.
Makeup Water Treatment

The makeup water quality is especially important with frequent startups/shutdowns,
because of the additional water usage required during these operations. The makeup
water limits provided in the phosphate(3), AVT(4) and OT(5) guidelines are comparable to
the requirements for the condensate cycle.
Properly designed and operated makeup systems are generally reliable in providing a
product meeting the requirements of the plant with respect to both quantity and purity.
Unfortunately, the makeup system is sometimes taken for granted. During cycling and
peaking operations, it is vitally important that routine surveillance of the makeup plant
is maintained to meet standard makeup water quality requirements(6).
3-3

3.3 MONITORING IMPORTANCE AND REQUIREMENTS

Sampling and Monitoring
Monitoring of core parameters (see Table 1-1) is essential for transient operation.
During shutdown, additional monitoring of iron and copper, and monitoring of the
water treatment additives used during layup is necessary. Water chemistry and other
monitoring during layup is described in Section 4-6.
During startup, additional monitoring may include more frequent sampling for iron
and copper, analysis for organics, and analysis of the makeup and the condensate
storage tank water. Membrane Filter Charts and membrane filtering of feedwater have
been found to be a rapid and useful method of evaluating corrosion product transport
during start-up and re-starts(7). This is a very simple and available method which can
provide a direct indication of whether the shutdown and layup procedures have been
successful.
Sampling Problems
During low load operation, pressure and flow characteristics of the sampled streams
change and often there is insufficient sample flow to analyzers and grab sampling
ports. In improperly designed sampling systems, the changing sample flows can result
in sampling errors up to several hundred percent. The sampling system characteristics
need to be tested and the sampling system improved if necessary, particularly for
cycling and peaking units.
During startups, re-starts, rapid load changes, significant amounts of corrosion
(9-11)
products can be transported from the pre-boiler system to the boiler . After extended
outages and where systems have been opened for inspection and repair, the quantities
may be large (even in the ppm range). Figure 3-1 shows an example of iron and copper
levels measured at the economizer inlet of a drum unit startup(9,10). Thus, it is very
important to improve the sampling systems for cycling and peaking service in order
that a proper assessment of corrosion product transport to the boiler can be made
during this type of operation(8).
3-4

80
70
600
60
500
50
400
40
300
30
200
20
100
Copper Concentration (ppb)
Iron Concentration (ppb)
Iron
700
10
Copper
0
0
Time (hours)
Figure 3-1 Metals Concentrations in Feedwater During Startup Operations(9,10)
3.4 MAJOR CHEMICAL TRANSIENT

A major chemical transient might include a major condenser leak.
A small condenser leak of low solids water (cooling pond, river, etc.) would generally
permit continued operation while isolating the location of the condenser leak and for
making suitable repairs, such as plugging the offending tube(s).
The incidences of condenser leaks tend to increase during cycling operation.
A brackish or sea water leak presents a more difficult problem. The presence of
chlorides in the sea water, particularly magnesium chloride, will produce an acidic
condition in the boiler (hydrochloric acid) and cause severe tube damage via hydrogen
damage if allowed to continue for even short periods of time.
3-5

With the availability of a condensate polisher on the unit, an orderly shutdown may be
permitted during sea water leakage, especially if a deep bed polisher is provided, and
if the sea water leak is small. Utilities with deep bed polishers should retain one or
more beds in the hydrogen form to provide additional capacity to handle the condenser
leak.
Powdered resin condensate polishers contain less capability for removal of dissolved
impurities than deep bed polishers(2). If the leak is small, the use of powdered resin
systems may permit an orderly unit shutdown.
Chemistry monitoring is especially important when a sea water condenser leak is
suspected. Boiler water pH is critical and condensate cation conductivity and sodium
will assist in estimating the extent of the leak(8).
In any event, the unit should be shut down to repair the condenser leak. Depending on
an evaluation of cycle and boiler chemistry, the shutdown will be immediate or
orderly, as outlined above. If the unit has a divided waterbox then the load could be
reduced to half depending on the seriousness of the leak.
Chemical Transients and Equipment Failures

Chemical contamination may occur from several sources:
Makeup Demineralizer
Both caustic and acid contamination of the boiler have been reported as a result of
demineralizer regenerant solutions inadvertently entering the system through
equipment malfunctions or operator error.
Deep Bed Polisher
Contamination similar to that from the makeup demineralizer (above) can occur
and for the same reasons.
Chemical Cleaning
Acidic contamination has been reported after chemical cleanings because of

improper rinsing. Superheater contamination has been reported caused by
inadequate superheater isolation procedures.
Intrusion of chemical contamination from the above (and possibly other) sources
requires immediate unit shutdown, draining and flushing the unit. Inspection of
critical areas of the system (boiler, superheater, turbine, etc.) should be performed to
assess the effects of chemical intrusion on the system. Chemical cleaning of the boiler,
superheater and turbine may be required depending upon the results of the inspection.
3-6

Equipment repairs may also be required. In such case, a longterm layup will be
necessary. (See Layup Section 4.)
The use of a condensate/feedwater cleanup loop, such as shown in Figure 2-18, is
highly effective in removing contaminants from the cycle, permitting more rapid starts
and less contamination entering the boiler.
3.5 MINIMIZATION OF AIR IN-LEAKAGE

Minimization of air inleakage (oxygen and carbon dioxide) is essential to prevent
increased corrosion during startup. Oxygen and carbon dioxide can be controlled by
one or more of the following measures:
x
Makeup water deaeration
Protecting condensate storage tanks from air
Floating covers
Diaphragms
Nitrogen Purge
Maintaining condenser vacuum during shutdowns
Hotwell sparging
Use of a heat cycle deaerator
Proper maintenance procedures, particularly for equipment operating under

vacuum conditions
Optimization of air removal equipment
Steam or nitrogen blanketing steam-side surfaces during downtime periods
To minimize corrosion, the dissolved oxygen content at the economizer inlet and boiler
water during startup and before firing should be less than 100 ppb, the iron in the
feedwater should be less than 100 ppb and the copper in the feedwater should be less
than 10 ppb.
3-7

3.6 CORRECTIVE ACTIONS

Typical corrective actions to respond to out-of-specification steam and/or water
chemistry conditions for drum units on PT, EPT, AVT, OT and CT are presented in the
Corrective Actions sections of the respective EPRI guidelines(3-5,12). Individual
corrective action tabulations are given for the following:
x
Makeup treatment system effluent
Condensate storage tank effluent
Condenser leak detection trays
Air removal system exhaust
Condensate pump discharge
Deaerator inlet
Deaerator outlet
Economizer inlet
Boiler water
Reheat steam
For the specific suggestions during shutdown and startup, the reader is referred to
Sections 58 in this Guideline.
3.7 HOW TO USE THE PRESENT EPRI GUIDELINES FOR CYCLING

OPERATION
All the current EPRI Guidelines(3-5,12) for drum units present a series of curves for boiler
water concentrations of sodium, chloride, sulfate and silica vs. boiler drum pressure
which are considered satisfactory for normal operation, consistent with longterm
system reliability. The AVT Guidelines(4) also provide similar information for cation
conductivity. The Guidelines for once-through units also present normal operating
limits on cycle diagrams. Four additional action levels are also recognized:
x
Action Level 1
There is potential for the accumulation of contaminants and corrosion. Return
values to normal levels within 1 week.
3-8

x
Action Level 2
The accumulation of impurities and corrosion will occur. Return values to
normal levels within 24 hours.
Action Level 3
Experience indicates that rapid corrosion could occur, which can be avoided by
shutdown of the unit within 4 hours.
Immediate Shutdown (for drum units)

This action level is related to low pH, without regard to boiler pressure. Levels
of pH below 8.0 in the boiler water require immediate shutdown to prevent
rapid boiler tube damage.
Drum Units
For further guidance, maximum annual exposure to contaminant conditions are given
for both base-load and cycling units. The cumulative hours per year is a useful guide
for evaluating the operation of cycling units relative to water chemistry.
The following tabulation is an excerpt from the phosphate guidelines(3), and pertains to
both PT, EPT, AVT and oxygenated treated units with and without reheat:
Maximum Annual Exposure to Contaminant Conditions
Cumulative Hours per Year
Targets
Base Load
Cycling
Normal
Action Level 1
336
672
Action Level 2
48
96
Action Level 3
16
Immediate Shutdown
During cycling operation, a substantial time is spent at low load operation. A review of
the previously referenced curves of boiler water chemical concentration vs. pressure
indicates that boiler water chemical concentrations can be higher at these lower boiler
3-9

pressures. This relationship provides a further guide to water chemistry during startup
of drum units under PT, EPT, AVT, OT and CT. Chemical concentration curves for
variable pressures are included.
Once-Through Units
The maximum annual allowable exposure to contaminant conditions for once-through
boilers on both all-volatile treatment and oxygenated treatment is the same as that for
drum boilers.
Cycle diagrams for once-through boilers detailing chemistry limits are included in the
(4,5)
guidelines . If the guidelines cannot be met, then a thorough review of chemistry
operations, sampling and monitoring capabilities must be made.
3.8 OPERATING PROCEDURES

Cycling and peaking operations require careful control to prevent the formation of
corrosion products in the feedwater system. This can be accomplished with very close
control of out-of-service conditions especially the elimination of air ingress along with
proper chemistry control assessed by good sampling and monitoring protocols.
Particular attention of operators needs to be given to mixed-metallurgy feedwater
systems. Here it is extremely important that a reducing environment is present during
all periods of operation and shutdown. The reader is referenced to the latest
information on copper based alloys in the feedwater system(13).
Retrofit of a by-pass cleanup system with a condensate polisher is considered well
worth the expense as it shortens the startup (with fuel savings) as mentioned before by
making it possible to meet proper water chemistry conditions at acceptably low levels
of corrosion product transport. The means of justifying retrofitting condensate
(2,14)
polishers into fossil plants has recently been consolidated .
3.9 ENVIRONMENTAL CONSIDERATIONS

The effects of increased oxide generation removed by draining and increased
blowdown, disposal of layup chemicals, and increase in removal of volatile chemicals
through deaerator lines and condenser deaeration require special attention for their
handling and disposal. They must be addressed in relation to local and national
environmental regulations. Reduced control of corrosion product transport will
increase chemical cleaning frequencies with associated downtime and waste disposal
costs.
3-10

3.10 REFERENCES
1. ASME Handbook On Water Technology for Thermal Power Systems. ASME, United
Engineering Center, East 47th Street, New York, NY, 10017.
(a) Chapter 22 Postoperational Treatment, Lay-up, and Flushing
(b) Chapter 13 In-Cycle Processing Principals and Equipment
2. Condensate Polishing Guidelines. TR-104422. Palo Alto, Calif.: Electric Power
Research Institute, September 1996.
3. Cycle Chemistry Guidelines for Fossil Plants: Phosphate Treatment for Drum Units. TR103665. Palo Alto, Calif.: Electric Power Research Institute, December 1994.
4. Cycle Chemistry Guidelines for Fossil Plants, All-Volatile Treatment. EPRI TR-105041,
Final Report, April 1996.
5. Cycle Chemistry Guidelines for Fossil Plants, Oxygenated Treatment. EPRI TR-102285,
Final Report, December 1994.
6. Guidelines for Make-Up Water Treatment. EPRI GS-6699, March 1990.
7. Membrane Filter Comparison Charts, available from Babcock & Wilcox - Service
Technology, P.O. Box 351, 20 S. Van Buren Avenue, Barberton, Ohio 44203-0351.
8. Guideline Manual on Instrumentation and Control. CS-5164. Palo Alto, Calif.: Electric
Power Research Institute, April 1987.
9. J. Brown and P. McSweeney. Feedwater Line Corrosion. Proceedings of the
American Power Conference, Volume 39. 1977.
10. J. Brown and P. McSweeney. Feedwater Line Corrosion, Combustion, Volume 49,
No. 2, August 1977.
11. Mathews, J. The Importance of Start-up Chemistry to the Long-Term Reliability of
Power Generating Equipment. ASME Workshop on Improvement of Chemistry
Control During Start-up of Fossil Units, St. Louis, Mo. April 9-10, 1997.
12. Sodium Hydroxide for Conditioning the Boiler Water of Drum-Type Boilers. EPRI, TR105041, April 1996.
13. State-of-Knowledge of Copper in Fossil Plant Cycles. EPRI TR-108460, September 1997.
14. Cycle Chemistry Improvement for Fossil Power Plants. RP 2712-11, Palo Alto, Calif.:
Electric Power Research Institute.
3-11

3-12
4
SHUTDOWN AND LAYUP CONSIDERATIONS
COMMON TO MOST UNITS
4.1 INTRODUCTION
Severe corrosion damage to all power plant cycle components has been experienced
because of insufficiently protected metal surfaces during inactive periods. Examples of
such damage include the following:
x
turbine blade and disk pitting;
boiler drum and tube, feedwater heater, and condenser pitting and oxidation; and
stress corrosion of condenser and feedwater heater tubing in stagnant oxygenated

water.
Corrosion damage can occur on the water and steam-side surfaces as well as on other
surfaces, including pipe surfaces under insulation.
In addition to irreversible corrosion damage, the generation of excessive amounts of
metal oxides and the contamination of layup water, if used, with oxygen and carbon
dioxide adversely influence water and steam chemistry during subsequent startup and
operation. One commonly experienced effect of corrosion damage during layup is a
prolonged startup period. Other considerations of layup include its cost (chemicals,
equipment, manpower) and the proper disposal of layup water when practicing wet
layup and using chemicals such as ammonia and hydrazine.
The shutdown and layup periods should be viewed as a continuum of the good
practices used during operation. The primary purpose of the cycle chemistry is to
provide protective oxide surfaces on all components throughout the steam and water
circuits; the primary purpose of the shutdown and layup periods should be to maintain
those protective surfaces. A couple of examples will illustrate the guiding principles
for shutdown and layup:
4-1

Shutdown and Layup Considerations Common to Most Units
x
Use of OT with all-ferrous feedwater systems is to provide surfaces completely

protected by FeOOH. Thus during shutdown and layup those surfaces should not
be exposed to reducing chemistries by application of hydrazine or alternatives;
In contrast with mixed metallurgy feedwater systems, it is necessary to maintain

reducing conditions during operation so that cuprous oxide is the protective oxide
of choice. Thus during shutdown and layup these surfaces should not be exposed
to oxidizing chemistries.
Preventative measures for protecting steam cycle equipment during shutdown for
inactive periods, including short-term and longterm layup, are presented in this
section. More specific layup considerations are found in subsequent Sections
(phosphate treated unitsSection 5; AVT unitsSection 6; OT UnitsSection 7; caustic
treated unitsSection 8)
4.2 LAYUP PRACTICES

The procedures for layup of idle equipment fall into two general categories: the wet
and the dry procedures. In general, with the exception for units on oxygenated
treatment (OT), wet layup requires filling of most of the system with an alkaline
reducing solution (ammonia and hydrazine) and preventing air ingress by
pressurization with an inert gas (nitrogen). Dry layup requires drainage while hot, and
removal of all water followed by pressurization with a moisture-free inert gas or by use
of dehumidified air to maintain a low moisture environment. In selecting the proper
layup procedure for a specific boiler or steam generator and its related equipment, one
must consider the following(1):
x
the compatibility between the chemistry required for layup and that used during
operation;
maintenance of the protective oxides formed during operation;
the possibility the boiler or steam generator may be required for operation on short
notice;
facilities available for proper disposal of layup solutions;
the possibility of freezing;
a realistic assessment of the practicality of maintaining all the required conditions of

a given procedure, i.e., complete dryness in dry layup or completely filled reducing
conditions in wet layup (except for OT units);
local atmospheric conditions, e.g., salt air environment; and
4-2

x
the availability of sufficient high quality condensate, deaerated demineralized

water, nitrogen or dehumidified air during a unit outage.
A number of guidelines and other information have been published relative to

shutdown and layup and are available for review (2-7).
A comparison of the advantages and disadvantages for various shutdown and layup
alternatives is given in Table 4-1(18).
Short-term vs. Longterm Layup

Current layup practices vary widely, from the protection of all cycle components
during longterm layup, to providing no protection to any component. There should
not, however, be any difference in the degree of corrosion protection provided during a
short-term or longterm layup. The most significant differences between the two are in
the cost of layup chemicals, layup preparation, and maintenance.
For short-term layup periods, the following shutdown procedures have proven
effective:
x
Maintain condenser vacuum and turbine seals to protect the condensate system
from air ingress.
Provide auxiliary steam to blanket the deaerator. If auxiliary steam is unavailable,

pegging steam from an adjacent unit or from the drum should be provided. For
longer outages, nitrogen blanketing may be more convenient.
Nitrogen or steam blanket the boiler. The nitrogen or steam inerting systems
should be automatic with multiple injection points on the boiler, deaerator,
superheater and feedtrain vents. A unit with frequent shutdowns requires a fast
response system, thus indicating an automatic system.
For short outages, a turbine steam bypass system will permit the boiler to operate at a
low firing rate while taking the turbine off-line. This procedure may result in a net
energy savings while facilitating rapid return to service once load demand increases.
(8,9)
Several references can be consulted relative to these turbine bypass systems.
4-3

Table 4-1
Shutdown and Layup Alternatives Showing Advantages and Disadvantages for
Each Alternative
Advantages
Disadvantages
Wet storage with

ammonia/hydrazine
solution*
1. No concern about
relative humidity
2. Easily maintained
3. Easily tested
4. With proper
installation, leaks can
easily be detected
5. Superheaters and
reheaters may be
stored safely
6. If facilities are
installed, solution
may be reused
1. Possible pollution
when draining
2. Need to recirculate
regularly
3. Hydrazine possible
carcinogen
4. High water
consumption prior to
startup; solution must
be drained and
possibly rinsed
5. Regular monitoring
6. Excessive ammonia
must not be added if
copper or copper
alloys are present in
the system
7. Tight isolations are
prerequisite
8. Not recommended if
freezing may occur
9. Draining if work is to
be carried out
10. Pure water (demin)
must be used
Nitrogen
1. System need not be

completely dry
2. Completely
independent of
climatic conditions
3. May be used as a
capping of normal
operating fluid during
outages
1. Very dangerous;
asphyxiation of
workers if not
properly vented
before access
2. Preferably to be
carried out while
system is being
drained
__________________
*Requires nitrogen
blanket
4-4

Dry air
1. Readily available basic

constituent
2. Maintenance on plant
performed without
problems
3. Easy monitoring
4. No risk to personnel
5. Whole plant may be
stored dry if drainable
or dryable
6. Independent of
ambient temperature if
air dry enough
7. Residual heat in boiler
steelwork utilized for
drying
1. Drying equipment and

blowers required
2. Climatic conditions
may cause rapid
deterioration in storage
conditions
3. Hermetical sealing
may be required to
prevent 2, above
4. System must be
completely dry
5. Sediment may cause
corrosion if
hygroscopic
6. SO2 and dust must be
excluded from the air
used
7. If work to be carried
out on part of dried
system, that part of
system must be
isolated and redried
afterwards
8. Even draining hot and
under pressure does
not ensure complete
water removal
4-5

Some of the major advantages cited for turbine bypass systems are (10):
x
Flexibility of operation
Ability to hold the generator output during startup without undesirable turbine
cooling
Ability to recover following a load rejection before restarting or reloading the

turbine
Ability to match turbine metal temperatures on hot restart
Some of the disadvantages cited for turbine bypass systems are:

x
Increased plant cost
Complexity of control
Additional valve maintenance
Possibility of turbine or condenser damage from malfunction or failure of bypass

components
Increase in plant heat rate because of greater condenser heat loss during periods of
bypass system operation
Successful extended boiler layups have been accomplished using one of the following
options:
x
a wet layup with a pH of up to 10.0 achieved with ammonia, up to 200 ppm of

hydrazine, and condensate-quality water plus a pressurized nitrogen blanket.
(Note: The use of hydrazine is not recommended for units on oxygenated treatment.
Refer to Section 7 for recommendations for OT units.) Lower level reducing agent
treatments (for example 5-10 ppm hydrazine) have been found to be successful and
allow a quick return to service (See example in Section 4.7 and Step 6 in Section 4.8).
High concentrations of ammonia should be prevented from coming into contact
with copper alloys.
a wet layup with treated good quality boiler water of the same chemical
composition as that used during operation; or
a dry layup in which a hot boiler is drained and purged with nitrogen or
dehumidified air.
4-6

Good experience has been reported(12) for the second variant of wet layup of drum
boilers, utilizing a nitrogen blanket while maintaining the boiler water at the same
composition as during operation, without the need for the addition of a reducing agent.
With this procedure the individual boiler design must be carefully considered when
determining the number and location of nitrogen feed points: no boiler part at any time
should be exposed to vacuum. The multiple nitrogen feed points for this particular
application are illustrated in Figure 4-1; one feed point is not considered sufficient.
N2
N2
Superheater
Economizer
Economizer
Superheater
Superheater
N2
Waterwalls
Waterwalls
Figure 4-1 Nitrogen blanketing of a drum boiler showing the nitrogen

connections(12).
4-7

4.3 WET LAYUP (12-15)

Wet layup is a popular method of protecting a unit when it might have to be
returned to service on relatively short notice. It generally involves filling the unit with
demineralized water containing an excess of a reducing agent (oxygen scavenger).
Depending on design, the oxygen scavenger may be eliminated assuming a viable
nitrogen blanketing system is available. Circulation may be maintained, a head tank
may be used, or positive nitrogen pressure may be maintained throughout the
shutdown with water at normal operating levels. Wet layup can generally be used for
relatively short periods of up to 6 months although longer idle times may be
experienced.
Extensive use of nitrogen blanketing is recommended in conjunction with wet storage,
not only for the boiler, but also with other heat cycle components. Excellent layup
protection has been reported using a bulk nitrogen system comprised of liquid nitrogen
storage and provided with evaporators to convert the liquid nitrogen to gas.
A nitrogen cap:
x
Allows boiler and feedwater equipment to remain full
Requires no excessive addition of chemicals
Permits nitrogen to rush in when steam collapses, preventing oxygen from entering
the system.
The following procedures are utilized with a bulk nitrogen system:

Main Condenser and Turbine
x
Nitrogen addition starts while the turbine is still spinning down
Nitrogen is added quickly at first, then slowly as the vacuum approaches zero (The
condenser is the largest user of nitrogen)
Deaerator and Storage Tank

x
Nitrogen is added when the deaerator is still hot
Nitrogen is purged for about 20 minutes followed by the maintenance of a small

nitrogen positive flow
4-8

Feedwater Heaters
x
Nitrogen is supplied through a shell-side vent line
Steam Drum
x
Nitrogen enters the drum through vent lines
Nitrogen feed is started while the drum is still hot.
During wet layup, the oxygen scavenger concentration and the ORP must be
monitored. Also, the boiler and economizer waters should be circulated routinely to
prevent stagnant conditions developing.
Corrosion in the form of pitting frequently occurs under wet layup conditions due to
poor circulation of the treated water or failure to maintain a positive nitrogen pressure.
More serious is the fact that cracking has been found associated with welds in some
units. The cracking is the result of a corrosion fatigue mechanism similar to that found
in deaerators. The corrosion occurs during the layup period, with cracking following
soon after startup. Cracking has occurred around nozzles, particularly in the steam
drum but has been found, to a lesser extent, on the head to shell welds as well.
The use of a nitrogen cap, as outlined above, improves startup chemistry, reduces
layup corrosion, reduces boiler tube deposits and lengthens the time between chemical
cleanings.
Because nitrogen gas does not support human life, safety issues are very important.
Therefore, before any equipment that has been laid-up with nitrogen can be entered by
personnel, all nitrogen supply lines must be disconnected, the equipment purged with
air, and oxygen levels verified as safe by proper oxygen test procedures.
4.4 DRY LAYUP USING DEHUMIDIFIED AIR

The use of clean, dehumidified air to purge the boiler and auxiliary equipment during
layup periods is routinely practiced internationally, and is gaining in popularity in the
US for both long- and short-term layup periods.
The justification for the use of dehumidified air to protect ferrous surfaces is depicted
graphically in Figure 4-2, which is a plot of corrosion rate vs. humidity of air. This
graph illustrates that corrosion can be mitigated by maintaining air in contact with
corrosion prone surfaces at a relative humidity of 60% or less.
4-9
Corrosion Rate
20
40
60
Humidity of the air (percent)
80
100
Figure 4-2 Corrosion Rate of Steel Relative to Humidity of Air
A desiccant dehumidifier commonly used for layup of boilers and auxiliaries, is shown
in Figure 4-3(17). The dehumidifier consists of a wheel of ceramic material that has been
corrugated, so air can pass lengthwise down the fluted corrugations. A desiccant is
impregnated into the structure. Moisture is attracted from the air onto the desiccant as
the air passes through the wheel.
Other dehumidifier components include two fans, one each to pull the process and
reactivation air streams through the wheel, a drive motor to turn the wheel, and a
heater to warm the reactivation air so it can dry the desiccant. Finally, an electrical
control panel coordinates the operation of the fans, drive motor, and heater.
The wheel rotates slowly between two air streams (about one revolution every 10
minutes). The first air stream, called the process air, is dried by the desiccant. The
second air stream, which is heated and runs through the wheel in the other direction, is
called the reactivation air. Reactivation air transfers heat to the wheel, heating the
4-10

desiccant to remove and carry away its moisture so the desiccant can be reused to
collect more moisture from the process air.
The power system components must be made as air tight as possible. The dry air
circulation systems are then sized to provide
x
ten air changes per hour for water/steam-side components,
one air change per hour for flue gas-side components, and
five to ten air changes per hour for gas turbine components and generating
equipment.
If the installation does not allow the systems to be air-tight, larger values are used. If
the systems are exceptionally tight, smaller values can be used, or only a portion of the
circulating air can be processed through the dehumidifier.
Wet air
outlet
Reactivation air
inlet filter
Dry air outlet
Reactivation
fan
Reactivation
air heater
Reactivation
sector
Desiccant wheel
Humid air
inlet filter
Dry air fan
Figure 4-3 Rotary Desiccant Dehumidifier(17)
The system utilized to supply dry air to the various components of the feedwater,
steam and boiler circuits may be customized to adapt to various heat cycle
configurations. One example is the flow diagram depicted in Figure 4-4 (18).
4-11

LP
turbine
HP
turbine
Condenser
Boilers
Dehumidifier installed in
system to dry out and
circulate dehumidified
air to control relative
humidity <30%
Feed heating plant

LP
heaters
Feed
pumps
HP
heaters
Figure 4-4 Block Diagram of Dehumidifier Steam/Feed Cycle(18)
4-12

Another variation is shown in Figure 4-5(19). The flow path for Figure 4-5 can be
described as follows:
Dry air is discharged from the dehumidifier (DH) into the hotwell, and then flows
through the low pressure turbine and continues through all turbine sections to the
boiler, backward with respect to steam flow. Dry air flows through the feedwater side
of the heaters and is discharged out of the system, back to the DH. Condensate pumps
receive dry air from the hotwell and discharge it back to the DH from the discharge
check valves. Extractions are left open so dry air can reach the feedwater heaters, from
which air is returned to the DH. Drip pumps and crossover heaters are protected in the
same manner. Dry air is extracted from each waterwall header and returned to the DH.
Air moisture levels should be checked as air enters and as it exits the reheat section.
Two humidistats are installed in the return plenum of the steam side DH. They should
be set to turn the DH reactivation heaters and blower off when returning air humidity
decreases to 15% and turned on when it increases to 25%. (The percentage of time the
heaters stay off is a function of ambient humidity; the approximate on time is about
40%.)
HP turbine
LP turbine
IP turbine
Boiler
Cond
pumps
Feedwater
heaters
Steam
side D.H.
unit
S.H. drain
Hot
well
BFP
BFP
XO
HP
IP
LIP
LP#3
LP#2
LP#1
Gland
cond
Process air discharge

Process air return
Figure 4-5 Steamside Dehumidification Flow(19)
4-13

One report(26) notes that it is difficult to dry a system with hanging superheaters
(vertical tubes with bends) by the use of dehumidified air circulation. The same
difficulty is noted for non-drainable headers or connecting lines. The following drying
procedure was recommended for these instances:
Dry the systems by utilizing the standard vacuum equipment supplied with the
generating unit. The use of additional heating (operating the steam-heated air heater)
facilitates drying during the vacuum process. Vacuum drying is reported to be
complete within 10-36 hours, depending upon the unit. It is important that the vacuum
doesnt suck in any fireside environment (flyash and SO2)through small leaks, which
could lead to corrosive acids and salts.
(20)
Another customization involves blowing dry air through the turbine and boiler in the
opposite direction of normal steam and water flow. The air is dried by using a
commercial rotary-type air dryer (see Figure 4-3) capable of delivering a maximum
flow of 2250 scfm at a pressure of 13 inches (33 cm) of water.
The relative humidity is below 60% in less than 20 hours and less than 30% in 36 hours.
To ensure effective dehumidification, the boiler is flash drained at 250 psig (1.7 MPa)
drum pressure. Draining at 250 psig (1.7 MPa) pressure prevents condensation in the
secondary superheater and reheater U-bends in the hanging pendant sections.
Dehumidified air is discharged into the LP turbine as soon as the boiler steam drum
reaches atmospheric pressure. All turbine valves necessary to allow air flow through
the turbine steam cycle are opened. Low pressure turbine extraction piping and
heaters are dehumidified through the normal extraction piping, in the normal direction
of steam flow. Low point drains on the shell sides of the heaters are opened to facilitate
air flow.
The humidity is monitored at several locations to determine the status of the
dehumidification process. Relative humidity data indicates an adequate passivation in
most areas of the boiler-turbine cycle after 48 hours.
Additional applications of the use of dehumidified air for layup can be found in the
literature(21-24).
4.5 FEEDWATER HEATERS, CONDENSER, REHEATER AND TURBINE

Particular care must be exercised during shutdown and layup not only for the boiler,
but also for the remaining components of the heat cycle. Some considerations for the
remainder of these components follow.
4-14

These components are generally considered as a group, since they cannot be isolated
without special facilities being incorporated. These components are generally stored
dry. The reheater may be stored wet (for very longterm storage) when isolated from
the turbine (see later discussion of Figure 4-8), however a better practice is to store the
reheater dry, as wet conditions dissolve any salt deposits, leading to off-load corrosion
and pitting.
During major outages some utilities conduct a reheat soak with demineralized water to
dissolve any deposited salts. The process can be repeated until acceptable contaminant
limits are reached.
Turbine
An example of dry layup of a 515 MW turbine is shown in Figure 4-6(23). It is necessary
to preclude any steam ingress into the laid up turbine by installing additional vents
and drains (with a 8 in. (200 mm) siphon). The turbine has to be equipped with
additional connection points for dry air or venting. In this case(23), two air changes per
hour were sufficient for the steam turbine and condenser. In another example of dry
layup of a 107 MW turbine, Figure 4-7 shows the values of temperature and air
humidity when using two air dehumidifiers (one with 1.1 kW and one with 5.4 kW).
Turbine dry layup using dehumidified air can also be combined with dry layup of the
unit steamside circuits. Figures 4-4 and 4-5 show examples.
Non-return
flap removed
Heading line
H.P.
I.P.
L.P. 1
L.P. 3
L.P. 2
Condenser
Air
drier
Fresh
air
Fresh
air
Air
drier
Manhole
Closed
4-15

Figure 4-6 Turbine dry layup using dehumidified air (23)
35.5/18.2C
= 16%
37.0/18.3
= 14%
H.P.
I.P.
48.8/20.8C
= 5%
LP
21.2/10.8C
= 25%
56.5/22.1C
= 2%
Air drier
1.1 kW
29.7/18.5C
= 35%
30.7/16.0C
= 20%
Air drier
5.4 kW
23.8/16.5C
= 47%
18.2/10.2C
= 33%
18.3/10.2C
= 33%
Figure 4-7 Dry layup of 107 MW turbine showing measured values of temperature
(F/C) and air humidity
Feedwater Side of Condensers and Feedwater Heaters

The metallurgy of these components must be carefully considered when establishing
the feedwater chemistry for intermediate or long term storage. A recent EPRI
(15)
publication provides guidance for proper chemistry for mixed metallurgy systems.
For systems containing copper alloys, it is most important to maintain a reducing
environment (ORP < 0 mV) at all times to prevent excessive corrosion of the copper
alloys. This is generally accomplished by the use of hydrazine during layup.
Ammonia additions must be reduced to provide a pH of 9.0-9.2, and oxygen ingress
must be avoided. Hydrazine concentrations should be maintained at around 40-50
ppm for this application(16).
Shell Side Feedwater Heaters

The shell sides of feedwater heaters should be protected by a nitrogen blanket or a
steam blanket (short term layup) when the unit is out of service.
Superheater
If the superheater is stored wet, then it should be back filled with treated water of a
composition identical to that used for layup of the boiler. A nitrogen cap should be
used to prevent air ingress.
4-16

Deaerator and Storage Tank

The deaerator and deaerator storage tank should be protected by a steady, small
nitrogen purge.
4.6 LAYUP MONITORING

All layup conditions, dry or wet, should be either continuously or periodically
monitored to ensure that the layup water or air quality is maintained. Existing sample
points may be used to draw water samples for chemical analysis. Should the layup and
water chemistry deteriorate to corrosive conditions in a particular component, that
component should be drained and refilled with properly conditioned water, or
additional chemicals added, assuming proper mixing can be provided.
4.7 ENVIRONMENTAL CONSIDERATIONS

The disposal of layup solutions containing high concentrations of alkaline chemicals
such as ammonia, and/or high concentrations of reducing agents, such as hydrazine or
hydrazine substitutes, poses problems from an environmental standpoint. Solutions to
these problems may require modifications to existing waste treatment facilities. The
cooperation of regulatory authorities should be a part of the investigative process
necessary to resolve these environmental issues.
A low level chemical layup procedure(25) has been used to protect the environment by
not requiring draining of drum boilers prior to startup. This has been possible through
the use of adequate layup monitoring and an efficient nitrogen blanketing system. The
procedure is as follows:
With the boiler off-line, inject an oxygen scavenger at 5-10 ppm hydrazine equivalent
into the boiler when the boiler pressure decays to 200 psi (1.4 MPa) (typically 3 days).
The chemical injection is made using the normal chemical feed system. Natural boiler
circulation at 200 psi (1.4 MPa) is sufficient to mix adequately the chemicals with the
boiler water.
When the boiler decays to 5 psi (0.03 MPa) pressure (typically 7 days) a nitrogen cap is
applied to the boiler.
Upon return to service, the boiler is fired, without draining the layup solution, and the
drum vents are opened until 25 psi (0.2 MPa) is reached to remove excess ammonia
from the system.
Since it typically takes 3 days before the pressure decays to 200 psi (1.4 MPa), weekend
outages normally do not require a chemical injection treatment.
4-17

4.8 ROAD MAP FOR SHUTDOWN AND LAYUP

Figure 4-8 provides a generic road map for implementing shutdown and layup
procedures common to most units. Because of variations in design, some generating
units may require deviations to Figure 4-8, or may require customization to adapt to a
particular utilitys needs. Also please refer to Sections 5, 6, 7 and 8 for procedures
specific to phosphate, AVT, OT and CT respectively.
Step 1
Step 2
Short term shutdown
No
Intermediate and
long term
Wet layup
Yes
Yes
Maintain condenser
vacuum and turbine
seals
Yes
Evacuate reheater
with condenser
vacuum
Step 5
Step 6
Traditional
Yes
Inert the deaerator

and heater shells
Break reheater
vacuum with
Nitrogen purge
Inert the boiler with

automatic system
Low O2 scavenger
No
Dry layup
Yes
Step 3
Add 5-10 ppm

Hydrazine when boiler
pressure decays
to 200 psi (1.4 MPa)
Fill feedwater system

with 200 Hydrazine*
10 ppm Ammonia**
Add Nitrogen cap

when boiler pressure
decays to 5 psi
(0.03 MPa)
Establish boiler
Nitrogen cap of 5 psi
(0.03 MPa)
Maintain feed water

without change
Drain system to
remove all water
Yes
Drain system to
remove all water
Pressurize with N2 all

wetted parts
Follow Figures 4-4 and

4-5 or customize
Maintain small
Nitrogen flow through
condenser, turbine
and deaerator
Notes: *No Hydrazine for OT units

**Limit pH to 9.0 to 9.2 if units
have copper alloys in cycle;
maintain Hydrazine at
40-50 ppm
Back fill superheater

200 ppm Hydrazine*
10 ppm ammonia.
Nitrogen cap
Step 8
Very long term
storage
Yes
No
Step 4
No
Yes
Fill boiler with 10 ppm

Ammonia; and up to
200 ppm Hydrazine*
Drain condenser
under Nitrogen
Maintain chemical
limits per guidelines .
See sections 5, 6, 7,
and 8
Dry air
No
Isolate reheater
Backfill reheater and

superheater with 200
ppm Hydrazine*
10 ppm Ammonia
Nitrogen cap
Step 7
Add Nitrogen to condenser
while turbine spins down.
Maintain slow N2 flow.
Add Nitrogen to deaerator

and storage tank while still
hot.
Maintain slow N2 flow
Step 9
For maintenance:
purge with air all N2
from equipment to be
maintained.
Test to ensure safe
environment.
Maintain Nitrogen cap

on shell side of
feedwater heaters
Figure 4-8 Road Map to Develop Shutdown and Layup Guidelines Common to
Most Units
Notes: * No hydrazine for oxygenated units
**Limit pH to 9.0 to 9.2 if units have copper alloys in cycle;
maintain hydrazine at 40-50 ppm
4-18

Figure 4-8 is divided into 9 considerations, options or steps, which are further
described as follows:
Step 1Short-Term Layup
Short-term layup presumes that the unit will be required to operate within a relatively
short timeframe. In consideration of this, no major changes are required from normal
operating conditions, with the exception being that the unit must be protected from air
ingress. The condenser vacuum and turbine seals are maintained; the deaerator, heater
shells and boiler are inerted with nitrogen or steam; and, the feedwater chemistry is
maintained according to the requirements of the treatment philosophy employed (see
phosphate treatmentSection 5; AVTSection 6; oxygenated treatmentSection 7;
and caustic treatmentSection 8).
Step 2Intermediate and Longterm Layup Common to Dry and Wet Layup
Intermediate and longterm layup require additional steps to be taken to prevent
corrosion during intermediate periods of layup, such as for maintenance and
indeterminate cycling or peaking requirements; and during longterm layup for
indefinite periods of time. Certain procedures are common regardless of whether the
units are to be laid up dry or wet. There is a danger of off-load corrosion (pitting) if
there are salts present. Consideration needs to be given to whether the reheater
supports can take the weight if the reheater is to be filled with water.
During shutdown, the turbine, condenser (steam side) and reheater are generally
considered together because, unless special facilities are incorporated, there is no
practical way to isolate them. With special facilities incorporated, the reheater can be
isolated from the turbine and may be stored wet (see Step 8). The turbine, however,
can only be laid up dry as indicated previously in this section. The condenser may be
flooded and laid up wet, but several factors limit the feasibility of this procedure (10):
x
The condenser must be supported from the bottom to handle the extra weight of a
flooded condenser.
The expansion joints between the turbine and condenser are not designed to
support the weight of a flooded condenser.
A flooded condenser tends to pull the turbine bearings out of alignment.
Water in the condenser may cause moisture vapor to enter the turbine causing
corrosion.
For these reasons, the steam side of the condenser is normally laid up dry.
4-19

For Step 2, during shutdown, the reheater is evacuated by utilizing the vacuum in the
condenser. The vacuum is then broken using nitrogen pressure. The condenser is
drained under nitrogen.
If the turbine steam is supplied from a header system, all valves must be tight to
prevent moisture entrance into the turbine.
Step 3Dry Air Layup
The dry air layup procedure requires that all components of the system be drained.
There are several methods of maintaining dry air flow through the equipment, and
some of these are illustrated in Figures 4-4 and 4-7. The advantages and disadvantages
of dry air layup and the equipment required have been previously described in this
Section (Table 4-1).
Step 4Dry Layup with Nitrogen
Nitrogen can be used for blanketing equipment, which is drained but not completely
dry, or for blanketing equipment either filled with water or not, to prevent air ingress.
Step 4 is similar to Step 3, except nitrogen is used for a positive pressure on all
components rather than a dry air purge. A small continuous purge of nitrogen is
required, however, to protect the turbine, deaerator and deaerator storage tank.
Step 5Wet Layup: Traditional Method (Boiler and Feedwater Heaters)
The traditional method of wet layup involves filling the boiler, feedwater cycle and
superheater with demineralized water containing a volatile alkaline, reducing solution.
Up to 10 ppm of ammonia and up to 200 ppm of hydrazine have been used for this
purpose. However, for units on oxygenated treatment, hydrazine should be
eliminated.
For those units having copper alloy condenser tubes and/or feedwater heaters,
feedwater pH should be limited to 9.0 to 9.2 by reducing ammonia. Hydrazine is held
at 40-50 ppm. For these units, it is most important to maintain reducing conditions
(ORP < 0 mV) to prevent increased attack of the copper alloys associated with a change
(15)
of the surface oxide layers from cuprous to cupric oxide. .
A nitrogen cap of 5 psi (0.03 MPa) is maintained on the boiler.
Step 6Wet Layup: Low Oxygen Scavenger Method (Boiler and Feedwater Heaters)
Many alternatives to the traditional wet layup method have been used successfully by
markedly reducing the level of hydrazine. These procedures may not require boiler
4-20

draining prior to startup, thereby protecting the environment and not requiring special
disposal techniques or permits. In one procedure, 5 to 10 ppm of hydrazine equivalent
is injected into the boiler when the boiler pressure decays to 200 psi (1.4 MPa) (typically
3 days). The chemical injection is made using the normal chemical feed system.
Natural boiler circulation at 200 psi (1.4 MPa) is sufficient to mix adequately the
chemicals in the boiler water. No other changes need be made to the boiler or to the
feedwater chemistry. When the boiler pressure decays to 5 psi (0.03 MPa) (typically 7
days) a nitrogen cap is applied to the boiler.
Upon return to service, the boiler may be fired without draining the layup solution.
Also, since it typically takes 3 days before the boiler pressure decays to 200 psi (1.4
MPa), weekend outages normally do not require a chemical injection treatment.
Step 7Wet Layup (Balance of Cycle)
As the turbine spins down, nitrogen is added to the condenser, which also purges the
reheater system. A continuous purge of nitrogen is necessary to account for leakage
through the turbine steam seals.
Nitrogen is added to the deaerator and storage tank while this system is still hot. A
small flow of nitrogen is provided to purge this system.
A nitrogen cap is maintained on the shell side of the feedwater heaters. The
superheater is back filled with a solution of up to 200 ppm of hydrazine and 10 ppm
ammonia and a nitrogen cap maintained. (Units on oxygenated treatment will
eliminate the use of hydrazine for this application.)
Step 8Very Long Storage
For very long storage periods, the reheater is isolated from the turbine, and back filled
with a solution of up to 200 ppm hydrazine and 10 ppm ammonia, and capped with
nitrogen. The superheater is treated similarly.
Step 9Maintenance
Only equipment requiring maintenance should be drained (wet storage only), and
nitrogen (if used) purged with air to provide an environment suitable for entry of
personnel. Since nitrogen does not support human life, it is extremely important that
nitrogen is completely displaced by air. The atmosphere within the equipment to be
maintained should be tested with suitable test equipment to ensure the equipment is
safe for personnel entry.
4-21

4.9 REFERENCES
1. The ASME Handbook on Water Technology for Thermal Power Systems. American
Society of Mechanical Engineers, New York, N.Y. 1989.
2. VGB Guidelines. Preservation of Power Plant Systems. VGB-R116H. VGB
Technische Vereiniging der Grosskraftwerksbetreiber, 1981.
3. EPRI Guidelines. Long-Term Layup of Fossil Plants. CS-5112. Palo Alto, Calif.:
Electric Power Research Institute, April 1987.
4. CEGB: Long Term Storage of Power Plants. General Considerations and
Preservation Techniques. April 1978.
5. Guidelines for the Long-Term Storage of Power Plants. ESKOM. Ref. NWG7021.
August 1991.
6. Monitoring Cycle Water Chemistry in Fossil Plants, GS-7556, Volume 2. Palo Alto,
Calif.: Electric Power Research Institute, October 1991.
7. Cycle Chemistry Improvement for Fossil Power Plants. Electric Power Research
Institute, Palo Alto, Calif.: TR-104422, September 1996.
8. D. D. Rosard and T. McCloskey. Bypass Systems Increase Cycling Capability of
Drum Boilers, Power, July, 1984.
9. J. Reasons. Steam Bypass Systems for Drum Boilers. How Much Capacity Do You
Need, Power, July, 1984.
10. D. B. DeWitt-Dick. Protection of Utility Steam Generating Systems During Idle
Periods, A.S.M.E. Workshop Improvement of Chemistry Control During Startup
of Fossil Units, April 9th and 10th, 1997, St. Louis, Missouri.
11. Combustion Fossil Power, J. Singer, Editor. Published by Combustion
Engineering, Inc./ASEA Brown Boveri, 1991.
12. A. Bursik and R. Richter. Hints for the Steam Generator Layup Practice (in
German). VGB Kraftwerkstechnik Vol. 60, No. 9, pp. 714-718.
13. R. J. Twigg. MothballingThe Impossible Solution? Fossil Plant Layup and
Reactivation Conference. EPRI TR-101250, October 1992.
4-22

14. W. Turowski and D. Daniels. Routine Use of Nitrogen Caps, A.S.M.E. Workshop
Improvement of Chemistry Control During Startup of Fossil Units, April 9th and
10th, 1997, St. Louis, Missouri.
15. State-of-Knowledge of Copper in Fossil Plant Cycles. TR-108460, Palo Alto, CA: Electric
Power Research Institute, September 1997.
16. S. R. Pate and R. C. Turner. Minimizing Corrosion Product Transport at Georgia
Power. ASME Workshop, St. Louis, MO, Apr. 9-10, 1997.
17. D. Kosar. Power Plant Preservation Using Desiccant Dehumidifiers. Fossil Plant
Layup and Reactivation Conference. EPRI TR-101250, October 1992.
18. J. Jenkins and T. Moss. The Storex Project. Fossil Plant Layup and Reactivation
Conference. EPRI TR-101250, October 1992.
19. D. B. Griffin and H. D. Thomas. Fossil Plant Layup and Unanticipated
Reactivation. Fossil Plant Layup and Reactivation Conference. EPRI TR-101250,
October 1992.
20. M. E. Walker. Passivation of Unit 3 State Line Station Through Dehumidification.
Fossil Plant Layup and Reactivation Conference. EPRI TR-101250, October 1992.
21. T. Gostenkors. Layup of Units in Power Station Gersteinwerk (in German). Der
Maschinenschaden, Vol. 49, No. 6, p. 236ff, 1976.
22. W. Kahlert, Fast Startup Procedure for Standby Units in the VEW Power Station
Gersteinwerk (in German). VGB Kraftwerkstechnik, Vol. 52, No. 5, p. 425ff, 1972.
23. H. Steger. Standby Corrosion Prevention in Power Plants (in German). Der
Maschinenschaden, Vol. 49, No. 1, pp. 23-27, 1976.
24. T. H. Pike. Corrosion Prevention of Turbines During Extended Outages (Case
Histories. Proceedings of the 48th International Water Conference, Pittsburgh, PA, No.
2-4, 1987.
25. W. H. Stroman and N. L. Rentle. Declining Pressure Method for Boiler Storage
and Boiler Cleanliness Assessment by Ultrasonic Technique at San Diego Gas and
Electrics South Bay Unit 4, Fossil Operations and Maintenance Information
Services, Clearwater Beach, Florida, June 15-18, 1992.
26. VGB Guidelines, Layup of Power Plants, VGB-R116H, VGB Kraftwerkstechnik
GmbH, Essen, 1983.
4-23
5
PHOSPHATE TREATED DRUM UNITS
5.1 INTRODUCTION
The utilization of phosphate salts for internal boiler water treatment is more than 70
years old. During this time there have been several philosophies developed relative to
the proper use and proper concentration of phosphates in the boiler drum. Also, there
have been problems reported with these various treatments, notable of which are
phosphate hideout, caustic gouging, hydrogen damage, and acidic phosphate under
deposit corrosive attack. These problems have been related to the older treatment
methods of coordinated phosphate treatment and congruent phosphate treatment, as
depicted in Figure 5-1.
To mitigate these problems, two new phosphate treatment approaches have been
(1)
identified as phosphate treatment (PT) and equilibrium phosphate treatment (EPT), as
depicted in Figure 5-2. For PT, the treatment philosophy involves broadening of the
control range above the sodium-to-phosphate 2.8 molar ratio curve, and allows
operation with up to 1 ppm of free sodium hydroxide. For EPT, the treatment
philosophy involves operations at or below phosphate levels which would lead to
hideout. A comparison of PT, EPT and the more familiar congruent phosphate
treatment (CPT) is shown in Figure 5-2.
The phosphate guidelines(1) require a lower feedwater pH for mixed metallurgy
systems than for all-ferrous systems. Also, while there are reports of successful
operation of all-ferrous systems with reduced or even no hydrazine in the feedwater(2),
it is most important to provide reducing conditions (ORP < 0 mV) at all times in mixed
metallurgy systems(3) including the shutdown periods. Reducing conditions in mixed
metallurgy systems will prevent excessive corrosion of copper alloys. The most
common method of ensuring reducing conditions is through the use of hydrazine in the
feedwater cycle.
The differences between all-ferrous and mixed metallurgy feedwater systems are
treated comprehensively in terms of startup, shutdown and layup in the drum unit
(Sections 6.3 and 6.4) for AVT. The reader is referenced to these sections for further
information which are also directly applicable to phosphate treated units
5-1

Phosphate Treated Drum Units
5.2 CURRENT NORMAL OPERATING GUIDELINES

Cycle chemistry guidelines for fossil plants operating with phosphate treatment have
recently been published by EPRI(1). This publication provides chemistry guidelines for
the two phosphate treatments previously mentioned, PT and EPT. A road map has
been included in the Phosphate Guideline to allow utilities to develop the optimum
treatment for their units.
The new phosphate Guidelines present a series of curves for boiler water
concentrations of sodium, chloride, sulfate and silica vs. boiler drum pressure which
are considered satisfactory for normal operation, consistent with longterm system
reliability. A series of three additional action levels, and an immediate shutdown level
are also presented, and are described in Section 3.
Cycle diagrams present chemistry target values both for comprehensive monitoring
and for core parameters. Core parameters (Table 1-1) are defined as those sample
points used for routine chemistry monitoring and control, as differentiated from those
sample points which may be added for troubleshooting and/or plant commissioning.
For example, the core parameter cycle chemistry diagram for EPT for reheat units and
the associated pressure related curves for sodium, chloride, sulfate and silica are shown
in Figures 5-3 to 5-7. The diagrams for PT (both reheat and non-reheat) and the
remaining diagrams for EPT (non-reheat) are available in the phosphate guidelines(1).
5-2

10.0
4.0
3.0
Na/PO4 3.0 (TSP)
9.5
1.0
pH at 25C
Equivalent NaOH
Concentration (ppm)
2.0
0.4
0.3
9.0
0.2
8.5
0
5
6
ppm PO4
10
10
a) Operating range of boiler water on coordinated phosphate treatment

4.0
3.0
10.0
Na/PO4 3.0 (TSP)
Na/PO4 2.6
9.5
1.0
0.4
0.3
pH at 25C
Equivalent NaOH
Concentration (ppm)
2.0
9.0
0.2
8.5
0
ppm PO4
b) Operating range of boiler water on congruent
phosphate treatment
Figure 5-1 Older Forms of Phosphate Treatment
5-3

10.0
4.0
TSP + 1 ppm NaOH
PT
9.5
pH at 25C
1.0
EPT
CPT
9.0
0.4
0.3
Na: PO4 = 3.0

Na: PO4 = 2.8
Na: PO4 = 2.6
8.5
5
ppm PO4
0.2
10
Figure 5-2 Schematic of Operating Ranges of Boiler Water on Equilibrium

Phosphate Treatment (EPT), Congruent Phosphate Treatment (CPT) and
Phosphate Treatment (PT)(1). The CPT is shown to its maximum Na:PO4 molar ratio
of 2.8; the normal operating range is below the Na:PO4 molar ratio of 2.6.
5-4
Equivalent NaOH Concentration (ppm)
3.0
Figure 5-3 Cycle Chemistry Diagram for a Drum Unit on Equilibrium Phosphate Treatment (Plants With Reheat)Core Parameters Marked.
5-5

4.8
6.2
7.6
9.0
Drum Pressure (MPa)

10.3 11.7 13.1 14.5
15.8
17.2 18.6 19.6
20
15
Action level 3
10
9
8
7
6
Action level 2
Action level 1
Sodium (ppm Na)
3
Normal
2
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
600 700
900 1100 1300 1500 1700 1900 2100 2300 2500

Drum pressure (psia)
2400
2700 2850
Note: Use of phosphate treatment above 2400 psia should

be carefully evaluated during commissioning.
Figure 5-4 Equilibrium Phosphate Treatment: Boiler Water Sodium vs. Operating
Pressure (Plants With Reheat)
5-7
Drum Pressure (MPa)

4.8
6.2
7.6
9.0
10.3
11.7
13.1
14.5
15.8 17.2
18.6 19.6
3.0
2.0
1.5
1.0
0.9
0.8
0.7
0.6
0.5
0.4
Chloride (ppm Cl)
0.3
Action level 3
0.2
Action
level 2
Action
level 1
0.10
0.09
0.08
0.07
0.06
0.05
0.04
Normal
0.03
0.02
0.01
600 700 900
1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
Pressure (psia)
Figure 5-5 Equilibrium Phosphate Treatment: Boiler Water Chloride vs. Operating
5-8

4.8
6.2
7.6
9.0
Drum Pressure (MPa)

11.7 13.1 14.5
10.3
15.8 17.2
18.6 19.6
3.0
2.0
1.5
1.0
0.9
0.8
0.7
0.6
0.5
Action level 3
0.4
Sulfate (ppm SO4)
0.3
0.2
0.10
0.09
0.08
0.07
0.06
Action
level 2
0.05
0.04
Normal
0.03
Action
level 1
0.02
0.01
600 700 900
1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
Drum Pressure (psia)
Figure 5-6 Equilibrium Phosphate Treatment: Boiler Water Sulfate vs. Operating
5-9
4.8
6.2
7.6
9.0
Drum Pressure (MPa)

11.7 13.1 14.5
10.3
15.8
17.2
18.6 19.6
20
15
10
9
8
7
6
5
4
3
Action level 3
Silica (ppm SiO2)
1.0
0.9
0.8
0.7
0.6
0.5
0.4
Action
level 2
0.3
0.2
Normal
Action
level 1
0.10
0.09
0.08
0.07
0.06
0.05
0.04
0.03
600 700 900
1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
Figure 5-7 Equilibrium Phosphate Treatment: Boiler Water Silica vs. Operating
5-10

5.3 STARTUP PROCEDURES

Section 3 explains how the chemistry curves and action levels can be utilized during
unit startup. Basically, during startups, the initial lower boiler pressure permits boiler
water chemical concentrations to be higher than those at normal unit operating
pressures. Also, the cumulative operating hours per year for which the various action
levels can be exceeded are twice the values for cycling units as compared to base
loaded units.
A road map for startup of PT or EPT units is given in Figure 5-8.
Is
system
full?
No
Fill system
per phosphate
guidelines
Step 1
Proceed
with startup
Step 3
Yes
Is system filled with Step 2
low O2 scavenger
Yes
(Section 4)
No
Step 3
Is system filled Yes

with chemicals per
PO4 guidelines
No
Polishers?
Step 4
Drain system
under nitrogen
and fill per PO4
guidelines
Yes
Proceed with
cleanup loop
(Section 3)
Step 4
No
Low oxygen
scavenger
Section 4
Step 4
Reduce O2 to
100 ppb
Fe to 100 ppb
Cu to 10 ppb
Step 2
Fire boiler.
Open vents to 25
psi (0.17 MPa)
(Section 4)
Fire boiler
Step 4
Step 3
Monitor
Step 5
Maintain
Keep Na, SiO2,
temperature ramp
Cl and SO4 within
Step
Step
5 per boiler and
5 phosphate guideturbine MFGs,
lines by controlling
requirements
pressure and
blowdown
Step 6
Achieve full
pressure and full
load
Figure 5-8 Road Map for Startup of PT or EPT Units
5-11
Road Map
The road map for startup of units operating with PT or EPT, Figure 5-8, can be divided
into 6 steps:
Step 1System Stored Dry
If the system has been stored dry (Section 4), it should be filled with water which meets
the EPRI Guidelines for PT or EPT units(1).
Step 2System Stored Wet: Low Oxygen Scavenger (Refer to Section 4)
If the system has been stored using the low oxygen scavenger procedure (Step 6 in
Section 4.8), the boiler can be fired immediately. The boiler vents are kept open to 25
psi (0.2 MPa) to remove any excess ammonia.
Step 3System Stored Wet: Excess Ammonia and Hydrazine (Refer to Section 4)
If the system has been stored wet with a surplus of ammonia and hydrazine, it must be
drained under nitrogen and refilled with water meeting the PT or EPT Guidelines (1).
(See Figure 5-3 for units operating with EPT). The startup of the unit can then proceed.
Step 4Cleanup and Firing Boiler
The following limits for the boiler feedwater are required prior to firing the boiler:
Oxygen d 100 ppb
Iron d 100 ppb
Copper d 10 ppb
During startup, the levels of corrosion products (iron and copper) can be very high
initially and silica may also be a problem.
Achieving the above limits is greatly facilitated through the use of condensate polishing
and/or condensate filtration (See Section 3). When these limits are attained, the boiler
can be fired.
Attainment of the prefiring limits will be more difficult in units not equipped with
condensate polisher and/or filtration equipment. Best control will require close
compliance with the guidelines for unit shutdown and layup.
5-12

Step 5Monitoring
After firing the boiler, monitoring must be fully implemented, both for chemistry
parameters, and to ensure that temperature ramps are maintained according to the
turbine and boiler manufacturers specifications.
During startup, the concentration vs. pressure curves can be utilized to control sodium,
silica, chlorides and sulfates (for example see Figures 5-4 to 5-7 for EPT, and the
(1)
phosphate guidelines for PT ). Boiler pressure should remain at reduced levels such
that these limits are maintained before pressure can be increased to the next stage.
Maximum use of blowdown and condensate polishing (if available) will minimize
startup times.
During startup, any chemical excursions must be dealt with quickly and effectively.
Increases in feedwater sodium and cation conductivity may indicate contamination
from the makeup system, contamination from chemical cleaning operations, condensate
polisher malfunction or, most likely, condenser leakage. The source must be found and
the problem corrected at once. Excursions affecting (lowering) boiler water pH must be
corrected immediately by feeding trisodium phosphate or 1-2 ppm of caustic.
Effects of cycle contamination are magnified at startup due to relatively low flow rates
for condensate, feedwater and steam. Cation conductivity may increase as a result of
air ingress due to either aeration of water during the shutdown period or air in-leakage
during startup. The change to boiler water chemistry will be minimal compared to
contamination involving the makeup system, chemical cleaning activities, condensate
polishers or condenser leaks.
Step 6Full Load
Full load can be achieved when chemical limits are within PT or EPT Guidelines(1).
5.4 CYCLING AND PEAKING UNITS

Cycling and peaking units have been previously defined (Section 3). These units are
subject to frequent startups and shutdowns, with generally short-term layup
procedures practiced, when required (see Section 4).
5.5 SHUTDOWN PROCEDURES

A road map for shutdown of PT or EPT units is presented in Figure 5-9. Shutdown
should be closely related to layup (Section 4) which in turn depends on the anticipated
outage length. Based upon this road map, shutdown should proceed in the following
manner:
5-13
Step 1
Normal cycling or
peaking load
reduction or
shutdown
Yes
Proceed with
shutdown for
short term layup
(Section 4)
Step 1
No
Step 2
Planned outage
Yes
No
Step 2
Unplanned outage
system or
No
equipment failure
Estimate outage
length - proceed with
short to long term
layup after adjusting
system chemistry
(See Section 4)
Step 2
Yes
No
Step 3
Chemical transient
Yes
Step 3
Condenser leak,
freshwater
Step 3
Yes
Isolate leak and

repair - usually while
system continues
to operate
No
Step 4
Yes
Orderly shut down

with polisher immediate without
Yes
Adjust boiler
pH to >8.0
Step 5
Orderly shutdown
with polisher
Step 5
Immediate
shutdown without
polisher
Step 5
Sea water?
No
Step 5
Chemical
intrusion
Figure 5-9 Road Map for Shutdown of PT or EPT Units

(This should be used in conjunction with Figure 4-8.)
5-14

Road Map
The road map for shutdown for PT and EPT units, Figure 5-9, should be used in
conjunction with Figure 4-8, Road Map to Develop Shutdown and Layup Guidelines
Common to Most Units. Figure 5-9 can be divided into 5 steps:
Step 1Normal Cycling or Peaking: Load Reduction or Shutdown
Normal cycling or peaking load reduction or shutdown presumes a short term layup as
described in Section 4.
An orderly reduction of load can be performed for routine cycling operations. Also, an
orderly reduction of load or unit shutdown can be performed when contamination is
minimal, as determined by chemical monitoring during such transients.
During orderly load reductions, the condensate cycle and boiler chemical limits should
be adjusted to conform with the phosphate chemistry guidelines(1) for PT or EPT, as
applicable. (Layup procedures are covered in Section 4 of this document.)
Particular care should be exercised to prevent oxygen ingress during this period, and
blowdown should be maintained at an appropriate level to remove contaminants from
the system.
During shutdown, any indication of phosphate hideout return (increased levels of
phosphate, change of pH, etc.) indicates that the boiler has not been operating at the
equilibrium level during normal operation. This should be corrected during normal
operation by following the procedure given in the phosphate guidelines to determine
(1)
the optimum (equilibrium) level of phosphate .
Step 2Outages
Planned or unplanned outages may be short or long term, depending upon system
demand or the extent of work required to return the unit to operation. The length of
time required for maintenance must be estimated and, depending upon this estimate,
short term or long term layup should be initiated (Section 4). Chemistry should be
adjusted prior to shutdown, as indicated in the various options delineated in Section 4,
Figure 4-8.
An unplanned outage due to an equipment or system failure can be treated as for a
planned outage.
5-15
Step 3Chemical Transients: Condenser Leak (Fresh Water)

For condenser leaks with fresh, relatively low solids cooling water, the leak can
generally be isolated and repaired while the unit is still operational under reduced load
(divided water box). Otherwise the unit should be shut down, and leaks isolated and
repaired.
Step 4Chemical Transients: Condenser Leaks (Sea Water)
Serious damage can occur to units within a short period of time with intrusion of sea
water. Without condensate polishing, the boiler must be shut down immediately upon
identifying a significant condenser leak. The addition of extra trisodium phosphate or
1-2 ppm of caustic may also be required as the boiler water pH drops.
With condensate polishing, the unit can generally be shut down in an orderly fashion,
especially if the polishers are of the deep bed type. With deep bed polishers, it is
prudent to maintain one or more vessels in the hydrogen form for added protection
against condenser leakage.
Powdered resin condensate polishers have less capability for removal of dissolved
impurities than deep bed polishers. If the leak is small, the use of powdered resin
Chemistry monitoring is especially important when a sea water condenser leak is
suspected. Boiler water pH is critical and condensate cation conductivity and sodium
will assist in estimating the extent of the leak.
an evaluation of cycle and boiler chemistry, the shutdown will be immediate or
orderly, as outlined above.
Substantial intrusion of sea water into the boiler will require that the unit be drained,
flushed and refilled with condensate quality water plus chemicals consistent with
operating requirements of PT or EPT, as applicable.
Step 5Chemical Transients: Chemical Intrusion
Some of the many causes of chemical intrusion (in addition to condenser leakage)
include:
x
Makeup water system malfunction
Polisher leakage
5-16

Poor regeneration
Acid or caustic contamination
Chemical cleaning residue; acid, caustic, other
Maintenance chemicals and preservatives
Silica from flyash or other contaminants from maintenance activities
Minor chemical intrusions can be controlled by increasing boiler blowdown, and

employment of idle condensate polishers, if available.
More serious chemical intrusions may require adjustment of boiler pH through
addition of more trisodium phosphate or 1-2 ppm of caustic. If these treatments are
unsuccessful, the unit must be shutdown (orderly with polisher, immediate without
polisher) if the pH falls below 8.0 (Figure 5-3). The unit then requires careful
inspection to determine possible damage, and the necessity for repair and possible
chemical cleaning prior to restart.
Intrusion of chemical contamination requires immediate unit shutdown, draining and
flushing the unit. Inspection of critical areas of the system (boiler, superheater, turbine,
etc.) should be performed to assess the effects of chemical intrusion on the system.
Chemical cleaning of the boiler, superheater and turbine may be required depending
upon the results of the inspection. Equipment repairs may also be required. In such
case, a longterm layup will be required. (See Section 4.)
During emergency shutdowns, such as for major sea water leaks and extensive
chemical contamination, immediate unit shutdown is required. Therefore, little can be
done to adjust cycle chemistry during shutdown since rapid action is required. During
such occasions, the unit should be drained, flushed and inspected to assess damages, as
outlined previously. Restarting the unit will be contingent upon this inspection, as will
layup provisions.
5.6 MIXED METALLURGY SYSTEMS

As mentioned in Section 4, the metallurgy of condensers and feedwater heaters must be
carefully considered when establishing chemistry parameters for startup, shutdown,
and layup. A recent EPRI report(3) on the State-of-Knowledge of Copper in Fossil Plant
Cycles describes the procedures required to prevent serious problems related to copper
alloy corrosion, such as copper volatilization and deposition. For systems containing
copper alloys, it is most important to maintain a reducing atmosphere (ORP < 0mV) at
all times. During operation this is generally accomplished by the use of suitable
concentrations of hydrazine with the addition of ammonia to regulate pH in the range
5-17
of 8.8-9.1. The reducing environment must also be maintained during the shutdown
and layup periods. Oxygen ingress must be avoided, as this will increase the corrosion
rate of copper alloys by changing the predominant surface oxide to cupric oxide.
The cycling of units, accompanied by periods of layup, materially increases the risk of
copper alloy attack, because of the opportunities for oxygen ingress with associated
increases of ORP into the oxidizing range. Therefore, chemistry control under these
conditions, requires much more attention than for base loaded units.
The reader is referred to Sections 6.3 and 6.4 for more comprehensive coverage of
mixed versus all-ferrous feedwater systems for drum units operating with AVT
feedwater.
5.7 CORRECTIVE ACTIONS

Typical corrective actions to respond to out-of-specification steam and/or water
chemistry conditions for PT and EPT units are presented in Section 6 of the phosphate
guidelines(1) (Corrective Actions). Individual corrective action tabulations are given
for the following:
x
Makeup treatment system effluent
Condensate storage tank effluent
Condenser leak detection trays
Air removal system exhaust
Condensate pump discharge
Deaerator inlet
Deaerator outlet
Economizer inlet
Boiler water
Reheat steam
5.8 LAYUP
Layup procedures are presented in Section 4, and a layup road map, which can be
applied to phosphate treated (PT) and equilibrium phosphate treated (EPT) units, is
5-18

depicted in Figure 4-8. Layup procedures fall into two categorieswet or dry. Within
each method, customization is possible (and encouraged) to suit the needs of the utility
or individual unit.
As described in Section 4, nitrogen blanketing for the boiler and feedwater system
components has been used to great advantage to prevent air ingress and subsequent
corrosion.
Particular attention should be given to maintaining proper layup conditions for the
turbine (Section 4).
Also, the use of minimal levels of hydrazine or hydrazine substitute, introduced into
the boiler upon layup has permitted unit startups without the necessity to drain and
refill. This procedure reduces startup time and is environmentally sound. This
procedure is referenced in Step 6 in Section 4.8.
5.9 REFERENCES
1. Cycle Chemistry Guidelines for Fossil Plants: Phosphate Treatment for Drum Units. TR103665. Palo Alto, Calif.: Electric Power Research Institute, December 1994.
2. B. Dooley, J. Matthews, R. Pate and J. Taylor. Optimum Chemistry for AllFerrous Feedwater Systems: Why Use an Oxygen Scavenger? IWC Paper I94-53,
International Water Conference, Pittsburgh, PA, Oct. 31Nov. 2, 1994.
3. State-of-Knowledge of Copper in Fossil Plant Cycles. TR-108460. Palo Alto, CA: Electric
Power Research Institute, September 1997.
5-19
6
ALL-VOLATILE TREATMENT
6.1 INTRODUCTION
All-volatile treatment must be used for once-through units, to avoid deposition of nonvolatile compounds in the boiler water/steam circuit. With the traditional form of
all-volatile treatment (AVT), ammonia and hydrazine is added to the feedwater to
provide chemical conditions that protect the feedwater heaters, boiler, superheaters,
reheaters and turbine against corrosion, without further chemical additions.
An alternative chemical treatment for once-through units is oxygenated treatment (OT see Section 7), where instead of hydrazine, oxygen is added in addition to the
ammonia. An intermediate form of conditioning is also being used, where only
ammonia, without hydrazine or oxygen, is added to the feedwater. With all three
alternatives, the degree of protection against corrosion provided by the chemical
additives is strictly limited. Therefore, it is essential to maintain high purity feedwater
and to prevent the ingress of impurities, both while on-load and during off-load
conditions.
All-volatile treatment can also be used for units with drum-type boilers, provided high
purity feedwater is available and the buildup of impurities in the boiler water is strictly
controlled. The absence of a solid alkalizing chemical in the boiler water gives less
protection against corrosion, but, because there should be lower concentrations of
impurities in the boiler water, it also reduces the risk of carrying over boiler water salts
and solid alkalizing chemicals into the steam. If the high purity feed and boiler water
conditions cannot be maintained during startup, operation and shutdown, it may be
necessary to resort to another form of chemical conditioning, such as phosphate or
caustic treatment. The Selection and Optimization document provides advice and
guidance on the optimum boiler water and feedwater choices for drum units(1).
Guidance on the use of AVT was given in the EPRI Interim Consensus Guidelines(2) in
1986. Cycle diagrams were provided for once-through and drum-type boilers with all
ferrous and mixed Fe-Cu metallurgy feedwater heating systems. The normal limits and
three action levels were given for sodium, chloride, sulfate, silica and cation
conductivities for feedwater and steam for once-through boilers. A range of pressures
was considered for drum boilers, with and without reheat, with additional pressure
curves for the normal limits and three action levels for sodium, chloride, sulfate and
6-1

All-Volatile Treatment
silica in the boiler water. In addition, some general guidance was also included on
startup, cycling and peaking operation.
The AVT guidelines for once-through and drum boilers were revised in 1996 (3) and
core parameters for a minimum level of instrumentation were given (Table 1-1), in
addition to the comprehensive list of parameters. Guidance was included for all-ferrous
and mixed Fe-Cu metallurgy for drum-type boilers, but was restricted to all-ferrous
feedwater heating systems for once-through boilers. Revised guidelines and action
levels were given and guidance was included on optimizing AVT.
Further minor revisions to the core parameters were incorporated in the EPRI report
on Selection and Optimization of Boiler Water and Feedwater Treatment of Fossil
Plants(1).
As an aid to planning and obtaining the optimum operating conditions for cycling,
startup, shutdown and layup, it is important to know as accurately as possible, what
notice will be given of shutdown, the period of outage and for startup.
6.2 ONCE-THROUGH UNITS

Current Guidelines
In considering cycling, startup, shutdown and layup of units operating on AVT, it is
assumed, in accordance with the latest EPRI Cycle Chemistry Guidelines(3), that the
units with once-through boilers under consideration have condensate polishing plants
and all-ferrous feedwater heating systems. The cycle diagram for all parameters
(including the core parameters) is given in Figure 6-1 for once-through units
operating with AVT.
Startup
During off-load conditions, deposited impurities may have been released into the
circuit or have entered from outside, e.g. condenser leaks, CO2 with air in-leakage.
Therefore, it is important to consider the effects on the feedwater and steam cation
conductivity, silica, sodium, chloride and sulfate concentrations during startup. If there
is a leak in the reheaters, CO2 and, more importantly, flyash and SO2, may be drawn in,
resulting in acidic condensed steam in the reheaters. There is some evidence that silica
is washed off turbines during shutdown and startup. Oxygen and hydrazine
concentrations in the feedwater require special consideration. Restrictions will need to
be applied to these parameters, but some relaxation from the normal EPRI guideline
values should be possible until steady state operating conditions are achieved. It should
be possible to eliminate hydrazine entirely, for once-through units with all-ferrous
feedwater heating systems(1) (see also Section 7 - Oxygenated Treatment).
6-2
Reheat Steam
Target
Sample
12
> 12
0.15
0.2
0.3
> 0.65
10
20
40
> 40
Chloride, ppb
12
> 12
Sulfate, ppb
12
> 12
Low-Pressure Steam (Optional)
Total organic carbon, ppb
100
> 100
Target
Parameter
CR
Sodium, ppb
CR
Cation conductivity,
S/cma
Silica, ppb
Specific conductivity
Air Removal System Exhaust

Target
Parameter
Parameter
Sample
>1
Air inleakage,
scfm/100 MWe
Injection
Dosage
< 20
Hydrazine, ppb
Condenser Leak Detection Trays or

Hotwell Zones (If applicable)
Makeup Treatment System Effluente
Target
Sample
Parameter
Cation conductivitya
or sodium
LP
turbine
IP
turbine
HP
turbine
Target
Parameter
Condensate
storage tank
Condenser
Economizer Inlet and Attemperation Water
Target Sample
Parameter
pHa
CR
CR
All ferrous metallurgy
9.2-9.6
< 9.2
> 9.6
Ammonia
Specific conductivitya
Cation conductivity, S/cma
0.15
0.2
0.3
> 0.65
Iron, ppb
>5
Copper, ppb
>2
Oxygen, ppb
1-10
15
20
> 20
Chloride, ppb
C or D
Deaerator
10
Specific conductivity,
S/cma
0.1
300
Condensate Storage Tank Effluent

Sample
N (aluminum
tanks only)
10
Target
Boiler
Parameter
LP
HP heaters
Sulfate, ppb
Silica, ppb
Makeup
treatment
system
Attemperat
Consistent with pH
Sample
Sodium, ppb
Condensate
polisher
Sodium, ppb
Condensate Pump Discharge

Target
Parameter
Sample
CR Sodium, ppb
CR S/cma
>3
Deaerator Outlet
Target
Parameter
Oxygen, ppb
Sample
< 10
Condensate Polisher Effluent
Deaerator Inlet
Hydrazine, ppb
Sample
< 20 ppb
Target
Sample
12
> 12
S/cma
0.15
0.2
0.3
> 0.65
Silica, ppb
10
> 10
Parameter
Target
Parameter
CR
Sodium, ppb
CR
Oxygen, ppb
0.3
0.3
200
> 200
20
40
Maximum Annual Exposure to

Contaminant Conditions
Targets
N (Normal)
Base Load
Cycling
1 (Action Level 1)
336 ( 2 weeks)
672 (4 weeks)
2 (Action Level 2)
48 (2 days)
96 (4 days)
3 (Action Level 3)
16
Immediate Shutdown
Legend
Footnotes
Sample Frequency
Target Values
C = continuous
S = grab, once per shift
D = grab, once per day
W = grab, once per week
T = troubleshooting and commissioning
N = Normal
1 = Action Level 1
2 = Action Level 2
3 = Action Level 3
a = Conductivity and pH measured at 25 C

e = Target values may be adjusted to reflect capabilities of installed equipment
Figure 6-1 Cycle Chemistry Diagram for a Once-Through Unit on All-Volatile Treatment
Sample and Chemical Feed Identification

CR = Record and alarm in Control Room
= Core parameter
= Continuous sample
= Chemical feed
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6-4
Step 1
No
Is system full?
Step 2
Yes
Step 4
Is system filled with

low O2 scavenger?
(Section 4)
Step 3
Fill system per

AVT guidelines
Yes
No
Safely vent N2 (if used)
Refill per AVT guidelines
Step 5

water per AVT
guidelines?
Reduce O2 to 100 ppb

and Fe to 30 ppb
Step 5
Yes
Proceed with
startup
Fire to boiler
Step 5
Step 6
Proceed progressively with

the polishers, deaerator,
economiser in cleanup loop
Monitor chemical
parameters
Step 6
Step 6
Maintain temperature ramp

within boiler and turbine
manufacturers requirements
Maintain Na, SiO2, pH, Cl,

SO4 and cation conductivity
within the AVT guidelines
Step 7
Achieve full pressure
and load
Figure 6-2 Startup of Once-through Units with All-Ferrous Feedwater Heaters
The steps are essentially similar to those described in Section 5 for phosphate treatment,
except that for once-through boilers, very high purity water is required for the boiler,
as well as for feedwater. Control of boiler water purity cannot be achieved by
blowdown, as is the case with drum boilers, and the absence of the reservoir of the
boiler and a steam separation stage in once-through boilers, means that the acceptable
level of impurities is much less than for drum boilers.
6-5
Step 1 - System Stored Dry

the EPRI Guidelines for once-through units operating on AVT (3).
Step 2 - Systems Stored Wet: Low Oxygen Scavenger
If the system has been stored using the low oxygen scavenger procedure (Section 4), the
boiler can be fired immediately.
Step 3 - System Stored Wet: Excess Ammonia and Hydrazine
If the system has been stored wet with a surplus of ammonia and hydrazine (Section 4),
it must be drained under nitrogen and refilled with water meeting the EPRI Guidelines
for once-through units operating on AVT(3).
Step 4 - System Stored using Nitrogen
If the system has been filled with nitrogen or filled with water, using nitrogen capping,
the nitrogen must be safely vented and the boiler refilled, if necessary, with water
meeting the EPRI Guidelines for once-through units operating on AVT(3). Startup of the
unit can then proceed.
Step 5 - Cleanup and Firing Boiler
Oxygen < 100 ppb
Iron < 30 ppb
During startup, the levels of corrosion products (iron) can be very high initially and
silica may also be a problem. Achieving these limits is greatly facilitated by using
condensate polishing (See Section 3). When these limits are attained, the boiler can be
fired.
Step 6 - Monitoring
boiler and turbine manufacturers specifications.
polisher malfunction or condenser leakage. The source must be found and the problem
corrected at once.
6-6
Step 7 - Full Load

Full load can be achieved when chemical limits are within the EPRI Guidelines for
once-through units operating on AVT(3).
Shutdown
Information is given in Section 4.8 on Shutdown and below for various planned
shutdown conditions.
Short shutdown (overnight/weekend) - No change to chemical conditions, leave plant
pressurized. Maintain condensate circulation and deaerator pressure. Raise the pH
when coming off-load.
Intermediate shutdown (weekend/week) - Leave plant pressurized, raise pH and the
hydrazine concentration (if used), when coming off-load.
Long shutdown (longer than 1 week) - Drain under nitrogen or from high temperature
(e.g. 130C) and maintain the boiler, superheaters and reheaters dry. Continue as
described under Layup.
Unplanned shutdowns also occur and, by their very nature, are unpredictable.
Therefore, it is difficult to give specific advice, except that, by using circulation,
endeavor to achieve the most appropriate conditions given above.
During shutdown, if there is a leak in the reheaters, CO2 and, more importantly, flyash
and SO2, may be drawn in, resulting in acidic condensed steam in the reheaters. There
is also evidence that silica is washed off turbines during shutdown.
A road map showing a scheme for shutdown of a once-through boiler operating with
AVT is given in Figure 6-3. The time taken to achieve stable shutdown conditions will
be plant dependent. This should be determined for each unit, as guidance for
subsequent shutdowns and amended in the light of operating experience.
The road map for shutdown of once-through units operating on AVT, Figure 6-3, can
be divided into 5 steps.
6-7
Step 1
Normal cycling and
peaking operation
Yes
No
Step 2
Step 2
Planned outage
Yes
No
Yes
Step 3
Isolate and repair
leak, usually allow
continued operation
Consider chemical
transients due to:Step 3
Yes
Condenser leak
fresh water cooling
No
Step 4
Orderly shutdown,
if polishers utilized,
otherwise
immediate shutdown
Estimate outage length.

Use layup appropriate
for duration of outage
Step 3
Step 2
Unplanned outage
Use short term

layup procedure
(Section 4)
Step 4
Yes
Condenser leak
sea water cooling
No
Step 5
Orderly shutdown, if
polishers utilized,
otherwise
immediate shutdown
Step 5
Yes
Chemical intrusion
Figure 6-3
AVT - Shutdown of Once-Through Units with All-Ferrous Feedwater Heaters
as well as the feedwater, and control of the boiler water purity cannot be achieved by
blowdown.
Step 1 - Normal Cycling or Peaking: Load Reduction or Shutdown
Normal cycling or peaking load reduction or shutdown presumes a short-term layup as
Step 2 - Outages
6-8
Planned or unplanned outages may be short or long term, depending on system

demand or the extent of the work required to return the unit to operation. The length of
time required for maintenance must be estimated and, depending on this estimate,
short term or longterm layup should be initiated (Section 4). Chemistry should be
adjusted prior to shutdown, as indicated in the various options delineated in Section 4.8
(Figure 4-8).
planned outage.
Step 3 - Chemical Transients: Condenser Leaks (Fresh Water)
For condenser leaks with fresh, relatively low dissolved solids cooling water, the leak
can generally be isolated and repaired, while the condensate polishing plant maintains
the feedwater quality.
Step 4 - Chemical Transients: Condenser Leaks (Sea Water)
water. With condensate polishing, the unit can generally be shut down in an orderly
fashion, especially if the polishers are of the deep bed type. With deep bed polishers, it
is prudent to maintain one or more vessels in the hydrogen form for added protection
Chemical monitoring is especially important when a sea water leak is suspected.
Sodium and cation conductivity will assist in estimating the extent of the leak.
an evaluation of the cycle chemistry, shutdown will be immediate or orderly, as
outlined above.
Substantial intrusion of sea water into the boiler will require that the unit is drained
and refilled with water meeting the EPRI Guidelines for once-through units operating
on AVT(3).
6-9
Step 5 - Chemical Transients: Chemical Intrusion

include:
x
Polisher leakage
Poor regeneration
Minor chemical intrusions can be controlled by employment of idle condensate

polishers, if available.
etc) should be performed to assess the effects of chemical intrusion on the system.
Chemical cleaning of the boiler, superheater and turbine may be required, depending
on the results of the inspection. Equipment repairs may be required. In such case, a
long term layup will be required. (See Section 4.)
done to adjust cycle chemistry during shutdown, since rapid action is required. During
such occasions, the unit should be drained, flushed and inspected to assess damage, as
layup provisions.
Cycling and Peaking

Special features may be required for once-through units to cycle, such as a turbine
bypass (Section 2).
As an aid to planning and obtaining optimum conditions, it is important to know as
accurately as possible, the frequency and duration of cycling and peaking, the notice
given and the variation of load patterns.
Essentially, cycling and peaking plant should operate according to the outline given
above for startup, load changes and shutdown.
6-10
Layup
Layup procedures are presented in Section 4 and a road map suitable for once-through
units operating on AVT is depicted in Figure 4-8.
Store under nitrogen or, if shutdown from a high temperature, maintain the boiler,
superheaters and reheaters dry. Possibly dehumidify the feedheaters or allow them to
remain wet. Avoid air ingress into the feedheaters. Monitor oxygen and pH, and
nitrogen and moisture, as appropriate.
The layup conditions are going to be dependent on the method of layup chosen. This
should be determined for each unit and each method of layup used. The information
obtained should then be used as guidance for subsequent repeat operations and
amended in the light of operating experience.
6.3 DRUM BOILERS WITH ALL-FERROUS FEEDWATER HEATING

SYSTEMS
In general, the features for the feedwater and steam for units with once-through boilers,
also apply to drum boilers. However, these need to be supplemented by additional
considerations for the boiler water. Some units with drum boilers may be equipped
with a condensate polishing plant, but many units are not and, therefore, will be more
susceptible to the effects of condenser leaks.
For completeness and ease of reference for AVT, phosphate treatments (Section 5), and
caustic treatment (Section 8), drum boilers with all-ferrous and mixed Fe-Cu
metallurgy feedwater heating systems are considered separately in the next two
sections.
Current Guidelines
The current guidelines for drum boilers with all-ferrous feedwater heating systems are
given in Figure 6-4 for units with reheat, including the core parameters. The normal
limits and three action levels for sodium, chloride, sulfate, silica and cation
conductivity in boiler water are given in Figures 6-5 to 6-9 for a range of operating
pressures. The values given for plants without reheat are twice those for plants with
reheat, except for pH, oxygen, TOC, iron and copper. They are not reproduced here
and reference should be made to the original documents(1,3).
6-11
Reheat Steam
Target
Parameter
Saturated Steam
Parameter
Sample
CR
Sodium, ppb
12
> 12
CR
S/cma
0.15
0.25
0.45
> 0.45
Silica, ppb
Sample
40
> 40
12
> 12
Sulfate, ppb
12
> 12
100
> 100
Chloride, ppb
Target
20
Sodium
Silica
Target
Injection
Dosage
Target
10

Parameter
Parameter
< 20
Hydrazine, ppb
Target
>1
Makeup Treatment System Effluent e
Target
Immediate
Shutdown
C or S
Chloride
Sulfate
C or S
<8
Oxygen
pHa
Cation conductivity a
or sodium
Phosphate
or NaOH
LP
turbine
IP
turbine
HP
turbine
Condensate
storage tank
Condenser
Attemperation
(See economizer inlet)
Blowdown
Makeup
treatment
system
Deaerator
Target
Parameter
Sample
Parameter
Sample
Sodium
Silica
CR

Boiler Water
(Blowdown or Downcomer)
Parameter
Sample
Air inleakage,
scfm/100 MWe
Sample
Sodium, ppb
Chloride, ppb
Sulfate, ppb
Silica, ppb
10
S/cma
0.1
300
Oxygen, ppb (When makeup

deaerated)
100
Boiler
Target
Parameter
pHa
CR
Sample
9.2-9.6
Mixed Fe-Cu metallurgy
8.8-9.1
< 9.2
> 9.6
< 8.8
> 9.1
Iron, ppb
>5
W
C
C
2
1-10
>2
15
20
> 20
10
20
> 20
Copper, ppb
CR
Oxygen,
ppb
All ferrous
Mixed Fe-Cu
Consistent with pH
0.2
0.35
0.65
Parameter
> 0.65
Oxygen, ppb
Sample
< 10
Sample
< 20 ppb
Target
CR
12
> 12
S/cm a
0.2
> 0.2
Silica, ppb
10
> 10
CR Sodium, ppb
CR
Sample
Target
Parameter
Condensate Polisher Effluent (If applicable)

Parameter
Target
Parameter
10
Sodium, ppb
Ammonia and
hydrazine
Deaerator Inlet
Hydrazine, ppb
Sample
Parameter
Condensate
polisher
Deaerator Outlet
Target
N (aluminum
tanks only)
Target
LP heaters
HP heaters
CR
Sample
>6
> 12
Plants with
polisher
Plants without
polisher
Plants with
polisher
Plants without
polisher
Sodium, ppb
12
0.3
> 0.3
0.2
0.35
0.65
> 0.65
200
> 200
Oxygen, ppb
20
40
> 40
S/cm a

Targets
N (Normal)
Base Load
Cycling
1 (Action Level 1)
336 ( 2 weeks)
672 (4 weeks)
2 (Action Level 2)
48 (2 days)
96 (4 days)
3 (Action Level 3)
16
Immediate Shutdown
Legend
Sample Frequency
C
S
D
W
T
= continuous
= grab, once per shift
= grab, once per day
= grab, once per week
= troubleshooting and commissioning
Footnotes
Target Values
N
1
2
3
= Normal
= Action Level 1
= Action Level 2
= Action Level 3

b = See curves of maximum allowable concentration versus pressure
c = Target values may be adjusted to reflect capabilities of installed equipment
d = See curves of allowable cation conductivity vs pressure
Figure 6-4 Cycle Chemistry Diagram for a Drum Unit on All-Volatile Treatment (Plants with Reheat)

= Core parameter
= Continuous sample
= Chemical feed
6.2
9.0
7.6
Drum Pressure (MPa)

10.3 11.7 13.1 14.5
15.8
17.2
18.6 19.6
2300
2500 2700 2850
Action level 3
10
9
8
7
6
Action level 2
5
4
Action level 1
3
Sodium (ppm Na)
2
Normal
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
900
1100
1300 1500
1700 1900 2100

Pressure (psia)
Figure 6-5 All Volatile Treatment: Drum Boiler Water Sodium vs. Operating
6-13
4.8
6.2
7.6
9.0
Drum Pressure (MPa)

11.7 13.1 14.5
10.3
15.8 17.2
18.6 19.6
3.0
2.0
1.5
1.0
0.9
0.8
0.7
0.6
0.5
0.4
Action level 3
Chloride (ppm Cl)
0.3
0.2
0.10
0.09
0.08
0.07
0.06
Action
level 1
Action
level 2
Normal
0.05
0.04
0.03
0.02
0.01
600 700 900
1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
Pressure (psia)
Figure 6-6 All-Volatile Treatment: Drum Boiler Water Chloride vs. Operating
6-14
4.8
6.2
7.6
9.0
Drum Pressure (MPa)

11.7 13.1 14.5
10.3
15.8 17.2
18.6 19.6
3.0
2.0
1.5
1.0
0.9
0.8
0.7
0.6
0.5
Action level 3
Sulfate (ppm SO4)
0.4
0.3
0.2
0.10
0.09
0.08
0.07
0.06
Action
level 2
0.05
0.04
Normal
0.03
Action
level 1
0.02
0.01
600 700 900
1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
Figure 6-7 All-Volatile Treatment: Drum Boiler Water Sulfate vs. Operating
6-15
4.8
6.2
7.6
9.0
Drum Pressure (MPa)

10.3 11.7 13.1 14.5
15.8 17.2
18.6 19.6
20
15
10
9
8
7
6
5
4
3
Action level 3
Silica (ppm SiO2)
1.0
0.9
0.8
0.7
0.6
0.5
0.4
Action
level 2
0.3
0.2
Normal
Action
level 1
0.10
0.09
0.08
0.07
0.06
0.05
0.04
0.03
600 700 900
1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
(Plants With Reheat)
6-16
4.8
6.2
7.6
9.0
Drum Pressure (MPa)

11.7 13.1 14.5
10.3
15.8
17.2
18.6 19.6
100
90
80
70
60
50
40
Action level 3
Cation Conductivity - S/cm
30
20
10
9
8
7
6
5
Action
level 2
Action
level 1
Normal
4
3
2
1
600 700 900
1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
Figure 6-9 All-Volatile Treatment: Drum Boiler Water Cation Conductivity vs.
Operating Pressure (Plants With Reheat)
6-17
Startup
During off-load conditions, impurities may have been released into the circuit or have
entered from outside, e.g. condenser leaks, CO2 with air ingress. Therefore, during
startup, it is important to consider the effects of these on the feedwater, boiler water
and steam cation conductivity, silica, sodium, chloride and sulfate concentrations
during startup. If there is a leak in the reheaters, CO 2 and, more importantly, flyash and
SO2, may be drawn in, resulting in acidic condensed steam in the reheaters. There is
some evidence that silica is washed off turbines during shutdown and startup. Oxygen
and hydrazine concentrations in the feedwater also require special consideration.
Restrictions will need to be applied to these parameters, but some relaxation from the
normal EPRI guideline values may be possible until steady state conditions are
achieved.
levels can be exceeded are twice the values for cycling units, as compared to base
loaded units.
If the boiler has been stored under nitrogen or filled with ammonia and hydrazine
solution, it is necessary to ensure that this is safely vented or disposed.
It is important to prevent high concentrations of oxygen and chloride in the boiler
water, as these can act synergistically and may initiate corrosion(4). For this reason, the
oxygen concentration of the boiler water should not be allowed to exceed 0.2 ppm
during boiler operation. It is also important to ensure that the pH, cation conductivity
and chloride concentration are within the limits given in the EPRI(1,3) guidelines for
boiler water. It might be possible to eliminate hydrazine in plants with all-ferrous
feedwater heating systems(1) (see Section 7 - Oxygenated Treatment).
Depending on the plant, and the shutdown and layup conditions adopted, several steps
will be required for startup (in addition to filling the boiler following a long shutdown
and safely venting the nitrogen, if used). The steps used during startup will be plant
specific and, depending on the practicality, the following stages should be monitored,
at least during a trial period:
6-18
Stage during Startup
Circuit Monitoring
a) Addition of hydrazine (if used) and

ammonia to the feedwater
pH, cation conductivity and oxygen
b) Additional boiler blowdown
pH, cation conductivity, chloride and

suspended corrosion products
c) Care to avoid additional carryover into

steam
Cation conductivity, silica and sodium
At full load, the normal EPRI guideline values given in Figure 6-4 should be achieved.
There may be room for relaxation, particularly, as regards silica in steam, during
startup and the earlier stages of operation and during low load operation, provided the
parameters are within the EPRI action levels 1-3, see Figures 6-5 to 6-9. The core
parameters, sodium, cation conductivity and oxygen, given in the EPRI guidelines(1,3)
should be monitored at the condensate pump discharge, condensate polisher outlet (if
installed), economizer inlet, boiler water (preferably at downcomer), including pH, and
steam. The normal operating levels, as given in the EPRI guidelines(1,3), should be
achieved as soon as possible. These are given in Figure 6-4.
A road map showing a scheme for startup of a drum boiler with an all-ferrous
feedwater heating system operating with AVT is given in Figure 6-10. The time taken to
achieve the required target values will be plant dependent. This should be determined
for each unit, used as guidance for subsequent startups and amended in the light of
operating experience. The procedure can normally be curtailed for warm and hot starts.
If the high purity feed and boiler water conditions cannot be maintained during
startup, it may be necessary to resort to another form of chemical conditioning, such as
phosphate or caustic treatment. The Selection and Optimization document provides
advice and guidance on the optimum boiler water and feedwater choices for drum
units(1).
6-19
Step 1
No
Is system full?
Step 2
Yes
Step 4

low O2 scavenger?
(Section 4)
Step 3
Fill system per

AVT guidelines
Yes
No

Drain storage solution
Step 5

water per AVT
guidelines?
Yes

and Fe to 100 ppb
Step 5
Proceed with
startup
Fire to boiler
Step 5
Step 6

polishers (if fitted), deaerator,
economiser in clean-up loop
Monitor chemical
parameters
Step 6
Step 6

within AVT guidelines by
controlling pressure and blowdown. Avoid excess carry-over
of impurities into steam

Step 7
and load
Figure 6-10 AVT - Startup of Drum Boilers with All-Ferrous Feedwater Heaters
6-20
The road map for startup of a drum-type unit operating on AVT with all-ferrous
feedwater heaters, Figure 6-10, can be divided into 7 steps.
except that higher purity water is required for units operating with AVT. Unlike oncethrough units operating on AVT, described in Section 6.2, control of boiler water purity
can be achieved by blowdown with drum units.
the EPRI Guidelines for drum units operating on AVT(3).
If the system has been stored using the low oxygen scavenger procedure (Section 4.8),
the boiler can be fired immediately.
If the system has been stored wet with a surplus of ammonia and hydrazine
(Section 4.8), it must be drained under nitrogen and refilled with water meeting the
EPRI Guidelines for drum units operating on AVT(3).
If the system has been filled with nitrogen or filled with water, using a nitrogen cap,
meeting the EPRI Guidelines for drum units operating on AVT(3). Startup of the unit can
then proceed.
Oxygen < 100 ppb
Iron < 100 ppb
condensate polishing (if fitted) (See Section 3). When these limits are attained, the boiler
can be fired.
6-21
Step 6 - Monitoring
silica, chloride and sulfate (for examples see Figures 6-5 to 6-9). Boiler pressure should
remain at reduced levels such that these limits are maintained before pressure can be
increased to the next stage. Maximum use of blowdown and condensate polishing (if
available) will minimize startup times.
corrected at once. Excursions affecting (lowering) boiler water pH must be corrected
immediately by feeding trisodium phosphate or 1-2 ppm of sodium hydroxide. Avoid
excess carryover of boiler water impurities into the steam.
Step 7 - Full Load
drum boilers operating on AVT(3).
Shutdown
Information is given in Section 4 on shutdown (see Figure 4-8) and below for various
planned shutdown conditions:
pressurized.
Intermediate shutdown (weekend-week) - Leave plant pressurized or store the boiler
under nitrogen.
Long shutdown (longer than 1 week) - Drain the boiler under nitrogen or blowdown
from high temperature (e.g. 130C, 266F) and maintain the boiler, superheaters and
reheaters dry. Continue as described under Layup.
6-22
A road map showing a scheme for shutdown of a drum boiler with an all-ferrous
achieve stable shutdown conditions will be plant dependent. This should be
determined for each unit, used as guidance for subsequent repeat operations and
Step 1
Normal cycling and
peaking operation
Yes
No
Step 2
Step 2
Planned outage
Yes
No
Yes
Step 3
Isolate and repair
leak, usually allow
continued operation
Yes
Condenser leak
fresh water cooling
No
Step 4
Yes
Condenser leak
sea water cooling
No
Step 5
Adjust pH >8.0, orderly
shutdown, if polishers
utilized, otherwise
immediate shutdown
Consider chemical
Step 4
Orderly shutdown,
otherwise
immediate shutdown

Step 3
Step 2
Unplanned outage
Use short term

layup procedure
(Section 4)
Step 5
Yes
Chemical intrusion
severely affecting pH
Figure 6-11 AVT - Shutdown of Units with Drum Boilers with All-Ferrous and
Mixed Metallurgy Feedwater Heaters
6-23
The road map for shutdown of a drum-type unit operating on AVT with all-ferrous
Again, the steps are essentially similar to those described in Section 5 for phosphate
treatment. Unlike once-through boilers operating on AVT, described in Section 6.2,
control of the boiler water purity can be achieved by blowdown with drum boilers.
be adjusted to conform with the AVT guidelines for drum units(3).
Particular care should be exercised to prevent oxygen ingress during this period and
the system.
Step 2 - Outages
Planned or unplanned outages may be short or longterm, depending on system
(Figure 4-8).
planned outage.
Step 3 - Chemical Transients: Condenser Leak (Fresh Water)
can generally be isolated and repaired, while the unit is still operational under reduced
load (divided water box) or if the condensate polishing plant (if fitted) maintains the
feedwater quality.
water. Without condensate polishing, the boiler must be shutdown immediately upon
6-24
identifying a significant condenser leak. The addition of trisodium phosphate or 1-2

ppm of sodium hydroxide may also be required as the boiler water pH drops.
With condensate polishing (if fitted), the unit can generally be shut down in an orderly
fashion, especially, if the polishers are of the deep bed type. With deep bed polishers, it
Chemical monitoring is especially important when a sea water leak is suspected. Boiler
water pH is critical, and sodium and cation conductivity will assist in estimating the
extent of the leak.
In any event, the unit should be shutdown to repair the condenser leak. Depending on
an evaluation of the cycle chemistry, shut down will be immediate or orderly, as
outlined above.
and refilled with water meeting the EPRI Guidelines for drum boilers operating on
AVT(3).
include:
x
Polisher leakage
Poor regeneration

More serious chemical intrusions may affect (lower) the boiler water pH, necessitating
adjustment of boiler water pH through the addition of trisodium phosphate or 1-2 ppm
6-25
sodium hydroxide. If these treatments are unsuccessful, the unit must be shut down
(orderly with polishers, immediate without polishers) if the pH falls below 8 (Figure
6-4). The unit then requires careful inspection to determine possible damage, and the
necessity for repair and possible chemical cleaning prior to restart.
layup provisions.
Cycling and Peaking

Essentially, cycling and peaking plants should operate according to the outline given
Layup
Layup procedures are presented in Section 4, and a road map suitable for units with
drum boilers operating on AVT is depicted in Figure 4-8.
Store the boiler under nitrogen or, if blowdown from a high temperature, maintain the
boiler, superheaters and reheaters dry. Possibly dehumidify the feedwater heaters or
allow them to remain wet. Avoid air ingress into the feedwater heaters. Monitor
oxygen and pH, and nitrogen and moisture, as appropriate. It is also possible to store
the boiler filled with a solution containing ammonia and hydrazine.
obtained should be used as guidance for subsequent repeat operations and amended in
the light of operating experience.
6-26
6.4 DRUM UNITS WITH MIXED METALLURGY FEEDWATER HEATING

SYSTEMS
EPRI(5) has recently produced a report on the State-of-Knowledge of Copper in Fossil
Plant Cycles as the first stage of the Program Copper project. This was in response to
a demand from members, particularly in the US, for improved performance of power
plants containing copper alloys. Traditionally, these have been widely used in
condensers, but, in some plants, brass and/or cupro-nickel have also been used for heat
exchange surfaces in low and high pressure feedwater heaters. Copper released from
feedwater heaters deposits in the boiler, increasing the locations where impurities can
concentrate on boiler waterwalls. Thick deposits can lead to overheating and the
presence of copper in deposits complicates chemical cleaning.
Copper in high pressure boilers can be carried over into the steam and deposited in
high pressure turbines, where even as little as 1 kg can reduce the output capacity of
the turbine by 1 MW. This is particularly true for plants operating at more than 2400 psi
(16.6 MPa) and is exacerbated further by increasing pressure. The presence of oxygen
and the absence of reducing conditions in the feedwater during all periods of operation
and shutdown is the main cause of copper transport round the circuit.
It is worth reiterating that startups are generally considered to be the periods of
maximum copper transport activity in the cycle. This relates directly to the feedwater
system not being protected during shutdown periods, i.e. that a reducing environment
(ORP < 0mV) is not maintained. Air in-leakage into the LP feedwater heating circuits
increases the growth of non-protective copper oxides and copper transport. The EPRI
Guiding Principles for successful operation of units with copper alloys(5) are:
x
Keep feedwater copper levels at guideline values (< 2 ppb at the economizer inlet)
during normal operation.
Establish conditions which favor cuprous oxide (Cu2O) rather than cupric oxide
(CuO) under all operating conditions.
Maintain reducing chemistry (oxidizing-reducing potential, ORP < 0mV) at all

times, including shutdown and startup.
Control feedwater pH in the range 8.8-9.1.
Implement shutdown procedures and layup programs which effectively minimize

copper transport activity upon return to service.
Consider volatility effects in controlling drum pressure; if possible, maximize

operating pressure in the range of 2400-2500 psi (16.5-17.2 MPa) and avoid overpressure operation above this range.
6-27
Current Guidelines
The current guidelines for drum boilers with mixed Fe-Cu metallurgy feedwater
systems are given in Figure 6-4 for reheat plants, including the core parameters. The
normal limits and three action levels for sodium, chloride, sulfate, silica and cation
pressures. Except for pH, oxygen, TOC, iron and copper, the limits for non-reheat plant
are generally higher by a factor of two. They are not reproduced here and reference
should be made to the original documents(1,3).
Startup
entered from outside, e.g. condenser leaks, CO2, with air ingress. Therefore, during
startup it is important to consider the effects of these on the feedwater, boiler water and
steam cation conductivity, silica, sodium, chloride and, sulfate concentrations. If there
is washed off turbines during shutdown and startup. Oxygen, hydrazine and copper
concentrations in the feedwater and copper concentrations of the steam will also
require special consideration, since the presence of oxidizing conditions increase the
release and transport of copper around the circuit.
water, as these can act synergistically and may initiate corrosion. For this reason, the
during boiler operation. The presence of oxygen also assists the transport of copper into
the steam, increasing the risk of deposition in the superheater and high pressure
turbine. It is also important to ensure that the pH, cation conductivity and chloride
concentration are within the limits given in the EPRI(1,3) guidelines for boiler water.
Hydrazine (or volatile reducing agents) should not be eliminated from plants with
mixed Fe-Cu feedwater heating systems.
Circuit Monitoring
a) Addition of hydrazine and ammonia to
pH, cation conductivity, oxygen and
6-28
the feedwater
copper


steam
Cation conductivity, silica, sodium and

copper
At full load, the normal EPRI guidelines values given in Figure 6-4 should be achieved.
parameters, sodium, cation conductivity and oxygen given in the EPRI(1,3) guidelines
steam, including copper. The normal operating levels, as given in the EPRI(1,3)
guidelines, should be achieved as soon as possible. These are given in Figure 6-4.
A road map showing a scheme for startup of a drum boiler with mixed Fe-Cu
for each unit, used as guidance for subsequent startups, and amended in the light of
The road map, Figure 6-12, can be divided into 7 steps.
loaded units.
If the high purity feed and boiler water conditions can not be maintained during
units(1).
can be achieved by blowdown with drum units. However, compared with units with
all-ferrous feedwater heating systems described in Section 6.3, additional
considerations are required for units with mixed Fe-Cu feedwater heaters. To reduce
the risk of copper corrosion and transport, the ingress of oxygen must be minimized
6-29
and chemically reducing conditions must be maintained during all periods of

operation, shutdown and layup.
Step 1
No
Is system full?
Step 2
Yes
Step 4

low O2 scavenger?
(Section 4)
Step 3
Fill system per

AVT guidelines
Yes
No

Step 5
Add N2H4, if necessary.
Reduce O2 to 100 ppb, Fe
to 100 ppb, Cu to 10 ppb

water per AVT
guidelines?
Step 5
Yes
Proceed with
startup
Fire to boiler
Step 5
Step 6

economizer in cleanup loop
Monitor chemical
parameters
Step 6
Step 6
Maintain Cu, Na, SiO2, pH, Cl,

controlling pressure and blowdown. Avoid excess carryover

Step 7
and load
Figure 6-12 AVT - Startup of Drum Boilers with Mixed Metallurgy Feedwater
Heaters
For ease of reference, full details of the steps for the startup of drum units with mixed
Fe-Cu feedwater heating systems, operating on AVT, are given below:
6-30

for drum units operating on AVT(3).
then proceed.
Oxygen < 100 ppb
Iron < 100 ppb
Copper < 10 ppb
initially and silica may also be a problem. Achieving these limits is greatly facilitated
by using condensate polishing (See Section 3). When these limits are attained, the boiler
can be fired.
Step 6 - Monitoring
6-31
During startup, the concentration vs. pressure curves can be utilised to control sodium,
immediately by feeding trisodium phosphate or 1-2 ppm of sodium hydroxide.
Avoid excessive carryover of boiler water impurities into the steam. This includes
copper, whose transport can be minimized by avoiding ingress of oxygen and
maintaining chemically reducing conditions.
Step 7 - Full Load
Shutdown
pressurized, avoid air ingress to the feedheaters.
under nitrogen. Avoid air ingress to the feedwater heaters.
from high temperature (e.g. 130C) and maintain the boiler, superheaters and reheaters
dry. Continue as described under Layup.
6-32
During shutdown. if there is a leak in the reheaters, CO2 and, more importantly, flyash
A road map showing a scheme for shutdown of a drum boiler with a mixed Fe-Cufeedwater heating system operating with AVT is given in Figure 6-11. The time taken to
The road map for shutdown of a unit with a drum boiler operating on AVT with mixed
metallurgy feedwater heaters, Figure 6-11, can be divided into 5 steps.
treatment, except that higher purity water is required for units operating with AVT.
Unlike once-through boilers operating on AVT, described in Section 6.2, control of the
boiler water purity can be achieved by blowdown with drum boilers. However,
compared with units with all-ferrous feedwater heating systems described in Section
6.3, additional considerations are required for units with mixed Fe-Cu feedwater
heaters. To reduce the risk of copper corrosion and transport, the ingress of oxygen
must be minimized and chemically reducing conditions must be maintained.
Particular care should be exercised to prevent oxygen ingress during this period to
minimize pickup of copper. Blowdown should be maintained at an appropriate level to
remove contaminants from the system.
6-33
Step 2 - Outages
adjusted prior to shutdown, as indicated in the various options deliniated in Section 4.8
(Figure 4-8).
planned outage.
feedwater quality.
extent of the leak.
outlined above.
AVT(3).
6-34

include:
x
Polisher leakage
Poor regeneration

(orderly with polishers, immediate without polishers). The unit then requires careful
layup provisions.
6-35
Cycling and Peaking

Layup
Layup procedures are presented in Section 4, and a road map suitable for drum boilers
operating on AVT is depicted in Figure 4-8.
allow them to remain wet. Avoid air ingress to the feedwater heaters, as this leads to
the increased corrosion of copper alloys, particularly in the presence of ammonia.
Monitor oxygen and pH, and nitrogen and moisture, as appropriate. It is also possible
to store the boiler filled with a solution containing ammonia and hydrazine. Avoid
contact of solutions with high ammonia concentrations with the copper alloys.
6.5 REFERENCES
1. Selection and Optimization of Boiler and Feedwater Treatment for Fossil Plants. Electric
Power Research Institute, Palo Alto, Calif. EPRI TR-105040. March 1997
Institute, Palo Alto, Calif. EPRI CS-4629. June 1986
3. Cycle Chemistry Guidelines for Fossil Plants: All Volatile Treatment. Electric Power
Research Institute, Palo Alto, Calif. EPRI TR-105041. April 1996
4. G. M. W. Mann and R. Garnsey, Waterside Corrosion Associated with Two-Shift
Boiler Operation on All-Volatile Treatment Chemistry. Corrosion 79 Conference.
Materials Performance, October 1980, pp 32-38
5. State-of-Knowledge of Copper in Fossil Plant Cycles. Electric Power Research Institute,
Palo Alto, Calif. EPRI TR-108460, September 1997
6-36
6
ALL-VOLATILE TREATMENT
6.1 INTRODUCTION
All-volatile treatment must be used for once-through units, to avoid deposition of nonvolatile compounds in the boiler water/steam circuit. With the traditional form of
all-volatile treatment (AVT), ammonia and hydrazine is added to the feedwater to
provide chemical conditions that protect the feedwater heaters, boiler, superheaters,
reheaters and turbine against corrosion, without further chemical additions.
An alternative chemical treatment for once-through units is oxygenated treatment (OT see Section 7), where instead of hydrazine, oxygen is added in addition to the
ammonia. An intermediate form of conditioning is also being used, where only
ammonia, without hydrazine or oxygen, is added to the feedwater. With all three
alternatives, the degree of protection against corrosion provided by the chemical
additives is strictly limited. Therefore, it is essential to maintain high purity feedwater
and to prevent the ingress of impurities, both while on-load and during off-load
conditions.
All-volatile treatment can also be used for units with drum-type boilers, provided high
purity feedwater is available and the buildup of impurities in the boiler water is strictly
protection against corrosion, but, because there should be lower concentrations of
impurities in the boiler water, it also reduces the risk of carrying over boiler water salts
conditions cannot be maintained during startup, operation and shutdown, it may be
necessary to resort to another form of chemical conditioning, such as phosphate or
caustic treatment. The Selection and Optimization document provides advice and
guidance on the optimum boiler water and feedwater choices for drum units(1).
Guidance on the use of AVT was given in the EPRI Interim Consensus Guidelines(2) in
1986. Cycle diagrams were provided for once-through and drum-type boilers with all
ferrous and mixed Fe-Cu metallurgy feedwater heating systems. The normal limits and
three action levels were given for sodium, chloride, sulfate, silica and cation
conductivities for feedwater and steam for once-through boilers. A range of pressures
was considered for drum boilers, with and without reheat, with additional pressure
curves for the normal limits and three action levels for sodium, chloride, sulfate and
6-1

silica in the boiler water. In addition, some general guidance was also included on
startup, cycling and peaking operation.
The AVT guidelines for once-through and drum boilers were revised in 1996 (3) and
core parameters for a minimum level of instrumentation were given (Table 1-1), in
addition to the comprehensive list of parameters. Guidance was included for all-ferrous
and mixed Fe-Cu metallurgy for drum-type boilers, but was restricted to all-ferrous
feedwater heating systems for once-through boilers. Revised guidelines and action
levels were given and guidance was included on optimizing AVT.
Further minor revisions to the core parameters were incorporated in the EPRI report
on Selection and Optimization of Boiler Water and Feedwater Treatment of Fossil
Plants(1).
6.2 ONCE-THROUGH UNITS

Current Guidelines
In considering cycling, startup, shutdown and layup of units operating on AVT, it is
assumed, in accordance with the latest EPRI Cycle Chemistry Guidelines(3), that the
units with once-through boilers under consideration have condensate polishing plants
and all-ferrous feedwater heating systems. The cycle diagram for all parameters
(including the core parameters) is given in Figure 6-1 for once-through units
operating with AVT.
Startup
During off-load conditions, deposited impurities may have been released into the
circuit or have entered from outside, e.g. condenser leaks, CO2 with air in-leakage.
Therefore, it is important to consider the effects on the feedwater and steam cation
conductivity, silica, sodium, chloride and sulfate concentrations during startup. If there
is washed off turbines during shutdown and startup. Oxygen and hydrazine
concentrations in the feedwater require special consideration. Restrictions will need to
be applied to these parameters, but some relaxation from the normal EPRI guideline
values should be possible until steady state operating conditions are achieved. It should
be possible to eliminate hydrazine entirely, for once-through units with all-ferrous
feedwater heating systems(1) (see also Section 7 - Oxygenated Treatment).
6-2
Reheat Steam
Target
Sample
12
> 12
0.15
0.2
0.3
> 0.65
10
20
40
> 40
Chloride, ppb
12
> 12
Sulfate, ppb
12
> 12
100
> 100
Target
Parameter
CR
Sodium, ppb
CR
S/cma
Silica, ppb
Specific conductivity

Target
Parameter
Parameter
Sample
>1
Air inleakage,
scfm/100 MWe
Injection
Dosage
< 20
Hydrazine, ppb

Target
Sample
Parameter
or sodium
LP
turbine
IP
turbine
HP
turbine
Target
Parameter
Condensate
storage tank
Condenser
Target Sample
Parameter
pHa
CR
CR
9.2-9.6
< 9.2
> 9.6
Ammonia
0.15
0.2
0.3
> 0.65
Iron, ppb
>5
Copper, ppb
>2
Oxygen, ppb
1-10
15
20
> 20
Chloride, ppb
C or D
Deaerator
10
S/cma
0.1
300

Sample
N (aluminum
tanks only)
10
Target
Boiler
Parameter
LP
HP heaters
Sulfate, ppb
Silica, ppb
Makeup
treatment
system
Attemperat
Consistent with pH
Sample
Sodium, ppb
Condensate
polisher
Sodium, ppb

Target
Parameter
Sample
CR Sodium, ppb
CR S/cma
>3
Deaerator Outlet
Target
Parameter
Oxygen, ppb
Sample
< 10
Deaerator Inlet
Hydrazine, ppb
Sample
< 20 ppb
Target
Sample
12
> 12
S/cma
0.15
0.2
0.3
> 0.65
Silica, ppb
10
> 10
Parameter
Target
Parameter
CR
Sodium, ppb
CR
Oxygen, ppb
0.3
0.3
200
> 200
20
40

Targets
N (Normal)
Base Load
Cycling
1 (Action Level 1)
336 ( 2 weeks)
672 (4 weeks)
2 (Action Level 2)
48 (2 days)
96 (4 days)
3 (Action Level 3)
16
Immediate Shutdown
Legend
Footnotes
Sample Frequency
Target Values
C = continuous
N = Normal
1 = Action Level 1
2 = Action Level 2
3 = Action Level 3

Figure 6-1 Cycle Chemistry Diagram for a Once-Through Unit on All-Volatile Treatment

= Core parameter
= Continuous sample
= Chemical feed
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6-4
Step 1
No
Is system full?
Step 2
Yes
Step 4

low O2 scavenger?
(Section 4)
Step 3
Fill system per

AVT guidelines
Yes
No
Step 5

water per AVT
guidelines?

and Fe to 30 ppb
Step 5
Yes
Proceed with
startup
Fire to boiler
Step 5
Step 6

the polishers, deaerator,
economiser in cleanup loop
Monitor chemical
parameters
Step 6
Step 6


within the AVT guidelines
Step 7
and load
Figure 6-2 Startup of Once-through Units with All-Ferrous Feedwater Heaters
as well as for feedwater. Control of boiler water purity cannot be achieved by
blowdown, as is the case with drum boilers, and the absence of the reservoir of the
boiler and a steam separation stage in once-through boilers, means that the acceptable
level of impurities is much less than for drum boilers.
6-5

the EPRI Guidelines for once-through units operating on AVT (3).
If the system has been stored using the low oxygen scavenger procedure (Section 4), the
boiler can be fired immediately.
for once-through units operating on AVT(3).
meeting the EPRI Guidelines for once-through units operating on AVT(3). Startup of the
unit can then proceed.
Oxygen < 100 ppb
Iron < 30 ppb
condensate polishing (See Section 3). When these limits are attained, the boiler can be
fired.
Step 6 - Monitoring
corrected at once.
6-6
Step 7 - Full Load

once-through units operating on AVT(3).
Shutdown
Information is given in Section 4.8 on Shutdown and below for various planned
shutdown conditions.
pressurized. Maintain condensate circulation and deaerator pressure. Raise the pH
when coming off-load.
Intermediate shutdown (weekend/week) - Leave plant pressurized, raise pH and the
hydrazine concentration (if used), when coming off-load.
Long shutdown (longer than 1 week) - Drain under nitrogen or from high temperature
(e.g. 130C) and maintain the boiler, superheaters and reheaters dry. Continue as
described under Layup.
A road map showing a scheme for shutdown of a once-through boiler operating with
AVT is given in Figure 6-3. The time taken to achieve stable shutdown conditions will
be plant dependent. This should be determined for each unit, as guidance for
subsequent shutdowns and amended in the light of operating experience.
The road map for shutdown of once-through units operating on AVT, Figure 6-3, can
be divided into 5 steps.
6-7
Step 1
Normal cycling and
peaking operation
Yes
No
Step 2
Step 2
Planned outage
Yes
No
Yes
Step 3
Isolate and repair
leak, usually allow
continued operation
Consider chemical
Yes
Condenser leak
fresh water cooling
No
Step 4
Orderly shutdown,
otherwise
immediate shutdown

Step 3
Step 2
Unplanned outage
Use short term

layup procedure
(Section 4)
Step 4
Yes
Condenser leak
sea water cooling
No
Step 5
Orderly shutdown, if
polishers utilized,
otherwise
immediate shutdown
Step 5
Yes
Chemical intrusion
Figure 6-3
AVT - Shutdown of Once-Through Units with All-Ferrous Feedwater Heaters
as well as the feedwater, and control of the boiler water purity cannot be achieved by
blowdown.
Step 2 - Outages
6-8
Planned or unplanned outages may be short or long term, depending on system

(Figure 4-8).
planned outage.
Step 3 - Chemical Transients: Condenser Leaks (Fresh Water)
can generally be isolated and repaired, while the condensate polishing plant maintains
the feedwater quality.
water. With condensate polishing, the unit can generally be shut down in an orderly
fashion, especially if the polishers are of the deep bed type. With deep bed polishers, it
Chemical monitoring is especially important when a sea water leak is suspected.
Sodium and cation conductivity will assist in estimating the extent of the leak.
outlined above.
and refilled with water meeting the EPRI Guidelines for once-through units operating
on AVT(3).
6-9

include:
x
Polisher leakage
Poor regeneration

layup provisions.
Cycling and Peaking

Special features may be required for once-through units to cycle, such as a turbine
bypass (Section 2).
6-10
Layup
Layup procedures are presented in Section 4 and a road map suitable for once-through
units operating on AVT is depicted in Figure 4-8.
Store under nitrogen or, if shutdown from a high temperature, maintain the boiler,
superheaters and reheaters dry. Possibly dehumidify the feedheaters or allow them to
remain wet. Avoid air ingress into the feedheaters. Monitor oxygen and pH, and
nitrogen and moisture, as appropriate.
obtained should then be used as guidance for subsequent repeat operations and
6.3 DRUM BOILERS WITH ALL-FERROUS FEEDWATER HEATING

SYSTEMS
In general, the features for the feedwater and steam for units with once-through boilers,
also apply to drum boilers. However, these need to be supplemented by additional
considerations for the boiler water. Some units with drum boilers may be equipped
with a condensate polishing plant, but many units are not and, therefore, will be more
susceptible to the effects of condenser leaks.
For completeness and ease of reference for AVT, phosphate treatments (Section 5), and
caustic treatment (Section 8), drum boilers with all-ferrous and mixed Fe-Cu
metallurgy feedwater heating systems are considered separately in the next two
sections.
Current Guidelines
The current guidelines for drum boilers with all-ferrous feedwater heating systems are
given in Figure 6-4 for units with reheat, including the core parameters. The normal
limits and three action levels for sodium, chloride, sulfate, silica and cation
pressures. The values given for plants without reheat are twice those for plants with
reheat, except for pH, oxygen, TOC, iron and copper. They are not reproduced here
and reference should be made to the original documents(1,3).
6-11
Reheat Steam
Target
Parameter
Saturated Steam
Parameter
Sample
CR
Sodium, ppb
12
> 12
CR
S/cma
0.15
0.25
0.45
> 0.45
Silica, ppb
Sample
40
> 40
12
> 12
Sulfate, ppb
12
> 12
100
> 100
Chloride, ppb
Target
20
Sodium
Silica
Target
Injection
Dosage
Target
10

Parameter
Parameter
< 20
Hydrazine, ppb
Target
>1
Makeup Treatment System Effluent e
Target
Immediate
Shutdown
C or S
Chloride
Sulfate
C or S
<8
Oxygen
pHa
Cation conductivity a
or sodium
Phosphate
or NaOH
LP
turbine
IP
turbine
HP
turbine
Condensate
storage tank
Condenser
Attemperation
Blowdown
Makeup
treatment
system
Deaerator
Target
Parameter
Sample
Parameter
Sample
Sodium
Silica
CR

Boiler Water
Parameter
Sample
Air inleakage,
scfm/100 MWe
Sample
Sodium, ppb
Chloride, ppb
Sulfate, ppb
Silica, ppb
10
S/cma
0.1
300
Oxygen, ppb (When makeup

deaerated)
100
Boiler
Target
Parameter
pHa
CR
Sample
9.2-9.6
8.8-9.1
< 9.2
> 9.6
< 8.8
> 9.1
Iron, ppb
>5
W
C
C
2
1-10
>2
15
20
> 20
10
20
> 20
Copper, ppb
CR
Oxygen,
ppb
All ferrous
Mixed Fe-Cu
Consistent with pH
0.2
0.35
0.65
Parameter
> 0.65
Oxygen, ppb
Sample
< 10
Sample
< 20 ppb
Target
CR
12
> 12
S/cm a
0.2
> 0.2
Silica, ppb
10
> 10
CR Sodium, ppb
CR
Sample
Target
Parameter

Parameter
Target
Parameter
10
Sodium, ppb
Ammonia and
hydrazine
Deaerator Inlet
Hydrazine, ppb
Sample
Parameter
Condensate
polisher
Deaerator Outlet
Target
N (aluminum
tanks only)
Target
LP heaters
HP heaters
CR
Sample
>6
> 12
Plants with
polisher
Plants without
polisher
Plants with
polisher
Plants without
polisher
Sodium, ppb
12
0.3
> 0.3
0.2
0.35
0.65
> 0.65
200
> 200
Oxygen, ppb
20
40
> 40
S/cm a

Targets
N (Normal)
Base Load
Cycling
1 (Action Level 1)
336 ( 2 weeks)
672 (4 weeks)
2 (Action Level 2)
48 (2 days)
96 (4 days)
3 (Action Level 3)
16
Immediate Shutdown
Legend
Sample Frequency
C
S
D
W
T
= continuous
= grab, once per shift
= grab, once per day
= grab, once per week
= troubleshooting and commissioning
Footnotes
Target Values
N
1
2
3
= Normal
= Action Level 1
= Action Level 2
= Action Level 3

b = See curves of maximum allowable concentration versus pressure
c = Target values may be adjusted to reflect capabilities of installed equipment
d = See curves of allowable cation conductivity vs pressure
Figure 6-4 Cycle Chemistry Diagram for a Drum Unit on All-Volatile Treatment (Plants with Reheat)

= Core parameter
= Continuous sample
= Chemical feed
6.2
9.0
7.6
Drum Pressure (MPa)

10.3 11.7 13.1 14.5
15.8
17.2
18.6 19.6
2300
2500 2700 2850
Action level 3
10
9
8
7
6
Action level 2
5
4
Action level 1
3
Sodium (ppm Na)
2
Normal
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
900
1100
1300 1500
1700 1900 2100

Pressure (psia)
Figure 6-5 All Volatile Treatment: Drum Boiler Water Sodium vs. Operating
6-13
4.8
6.2
7.6
9.0
Drum Pressure (MPa)

11.7 13.1 14.5
10.3
15.8 17.2
18.6 19.6
3.0
2.0
1.5
1.0
0.9
0.8
0.7
0.6
0.5
0.4
Action level 3
Chloride (ppm Cl)
0.3
0.2
0.10
0.09
0.08
0.07
0.06
Action
level 1
Action
level 2
Normal
0.05
0.04
0.03
0.02
0.01
600 700 900
1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
Pressure (psia)
Figure 6-6 All-Volatile Treatment: Drum Boiler Water Chloride vs. Operating
6-14
4.8
6.2
7.6
9.0
Drum Pressure (MPa)

11.7 13.1 14.5
10.3
15.8 17.2
18.6 19.6
3.0
2.0
1.5
1.0
0.9
0.8
0.7
0.6
0.5
Action level 3
Sulfate (ppm SO4)
0.4
0.3
0.2
0.10
0.09
0.08
0.07
0.06
Action
level 2
0.05
0.04
Normal
0.03
Action
level 1
0.02
0.01
600 700 900
1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
Figure 6-7 All-Volatile Treatment: Drum Boiler Water Sulfate vs. Operating
6-15
4.8
6.2
7.6
9.0
Drum Pressure (MPa)

10.3 11.7 13.1 14.5
15.8 17.2
18.6 19.6
20
15
10
9
8
7
6
5
4
3
Action level 3
Silica (ppm SiO2)
1.0
0.9
0.8
0.7
0.6
0.5
0.4
Action
level 2
0.3
0.2
Normal
Action
level 1
0.10
0.09
0.08
0.07
0.06
0.05
0.04
0.03
600 700 900
1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
(Plants With Reheat)
6-16
4.8
6.2
7.6
9.0
Drum Pressure (MPa)

11.7 13.1 14.5
10.3
15.8
17.2
18.6 19.6
100
90
80
70
60
50
40
Action level 3
Cation Conductivity - S/cm
30
20
10
9
8
7
6
5
Action
level 2
Action
level 1
Normal
4
3
2
1
600 700 900
1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
Figure 6-9 All-Volatile Treatment: Drum Boiler Water Cation Conductivity vs.
Operating Pressure (Plants With Reheat)
6-17
Startup
entered from outside, e.g. condenser leaks, CO2 with air ingress. Therefore, during
startup, it is important to consider the effects of these on the feedwater, boiler water
and steam cation conductivity, silica, sodium, chloride and sulfate concentrations
during startup. If there is a leak in the reheaters, CO 2 and, more importantly, flyash and
SO2, may be drawn in, resulting in acidic condensed steam in the reheaters. There is
some evidence that silica is washed off turbines during shutdown and startup. Oxygen
and hydrazine concentrations in the feedwater also require special consideration.
Restrictions will need to be applied to these parameters, but some relaxation from the
normal EPRI guideline values may be possible until steady state conditions are
achieved.
loaded units.
water, as these can act synergistically and may initiate corrosion(4). For this reason, the
during boiler operation. It is also important to ensure that the pH, cation conductivity
and chloride concentration are within the limits given in the EPRI(1,3) guidelines for
boiler water. It might be possible to eliminate hydrazine in plants with all-ferrous
feedwater heating systems(1) (see Section 7 - Oxygenated Treatment).
6-18
Circuit Monitoring
a) Addition of hydrazine (if used) and



steam
At full load, the normal EPRI guideline values given in Figure 6-4 should be achieved.
parameters, sodium, cation conductivity and oxygen, given in the EPRI guidelines(1,3)
steam. The normal operating levels, as given in the EPRI guidelines(1,3), should be
achieved as soon as possible. These are given in Figure 6-4.
for each unit, used as guidance for subsequent startups and amended in the light of
units(1).
6-19
Step 1
No
Is system full?
Step 2
Yes
Step 4

low O2 scavenger?
(Section 4)
Step 3
Fill system per

AVT guidelines
Yes
No

Step 5

water per AVT
guidelines?
Yes

and Fe to 100 ppb
Step 5
Proceed with
startup
Fire to boiler
Step 5
Step 6

economiser in clean-up loop
Monitor chemical
parameters
Step 6
Step 6

controlling pressure and blowdown. Avoid excess carry-over

Step 7
and load
Figure 6-10 AVT - Startup of Drum Boilers with All-Ferrous Feedwater Heaters
6-20
The road map for startup of a drum-type unit operating on AVT with all-ferrous
can be achieved by blowdown with drum units.
If the system has been stored wet with a surplus of ammonia and hydrazine
(Section 4.8), it must be drained under nitrogen and refilled with water meeting the
EPRI Guidelines for drum units operating on AVT(3).
If the system has been filled with nitrogen or filled with water, using a nitrogen cap,
then proceed.
Oxygen < 100 ppb
Iron < 100 ppb
condensate polishing (if fitted) (See Section 3). When these limits are attained, the boiler
can be fired.
6-21
Step 6 - Monitoring
immediately by feeding trisodium phosphate or 1-2 ppm of sodium hydroxide. Avoid
Step 7 - Full Load
Shutdown
pressurized.
under nitrogen.
from high temperature (e.g. 130C, 266F) and maintain the boiler, superheaters and
reheaters dry. Continue as described under Layup.
6-22
A road map showing a scheme for shutdown of a drum boiler with an all-ferrous
Step 1
Normal cycling and
peaking operation
Yes
No
Step 2
Step 2
Planned outage
Yes
No
Yes
Step 3
Isolate and repair
leak, usually allow
continued operation
Yes
Condenser leak
fresh water cooling
No
Step 4
Yes
Condenser leak
sea water cooling
No
Step 5
utilized, otherwise
immediate shutdown
Consider chemical
Step 4
Orderly shutdown,
otherwise
immediate shutdown

Step 3
Step 2
Unplanned outage
Use short term

layup procedure
(Section 4)
Step 5
Yes
Chemical intrusion
Figure 6-11 AVT - Shutdown of Units with Drum Boilers with All-Ferrous and
Mixed Metallurgy Feedwater Heaters
6-23
The road map for shutdown of a drum-type unit operating on AVT with all-ferrous
treatment. Unlike once-through boilers operating on AVT, described in Section 6.2,
control of the boiler water purity can be achieved by blowdown with drum boilers.
Particular care should be exercised to prevent oxygen ingress during this period and
the system.
Step 2 - Outages
(Figure 4-8).
planned outage.
feedwater quality.
6-24

extent of the leak.
In any event, the unit should be shutdown to repair the condenser leak. Depending on
an evaluation of the cycle chemistry, shut down will be immediate or orderly, as
outlined above.
AVT(3).
include:
x
Polisher leakage
Poor regeneration

6-25
(orderly with polishers, immediate without polishers) if the pH falls below 8 (Figure
6-4). The unit then requires careful inspection to determine possible damage, and the
necessity for repair and possible chemical cleaning prior to restart.
layup provisions.
Cycling and Peaking

Essentially, cycling and peaking plants should operate according to the outline given
Layup
Layup procedures are presented in Section 4, and a road map suitable for units with
drum boilers operating on AVT is depicted in Figure 4-8.
allow them to remain wet. Avoid air ingress into the feedwater heaters. Monitor
oxygen and pH, and nitrogen and moisture, as appropriate. It is also possible to store
the boiler filled with a solution containing ammonia and hydrazine.
6-26
6.4 DRUM UNITS WITH MIXED METALLURGY FEEDWATER HEATING

SYSTEMS
Copper in high pressure boilers can be carried over into the steam and deposited in
and the absence of reducing conditions in the feedwater during all periods of operation
and shutdown is the main cause of copper transport round the circuit.
It is worth reiterating that startups are generally considered to be the periods of
(ORP < 0mV) is not maintained. Air in-leakage into the LP feedwater heating circuits
increases the growth of non-protective copper oxides and copper transport. The EPRI
Guiding Principles for successful operation of units with copper alloys(5) are:
x



6-27
Current Guidelines
The current guidelines for drum boilers with mixed Fe-Cu metallurgy feedwater
systems are given in Figure 6-4 for reheat plants, including the core parameters. The
normal limits and three action levels for sodium, chloride, sulfate, silica and cation
pressures. Except for pH, oxygen, TOC, iron and copper, the limits for non-reheat plant
are generally higher by a factor of two. They are not reproduced here and reference
should be made to the original documents(1,3).
Startup
entered from outside, e.g. condenser leaks, CO2, with air ingress. Therefore, during
startup it is important to consider the effects of these on the feedwater, boiler water and
steam cation conductivity, silica, sodium, chloride and, sulfate concentrations. If there
is washed off turbines during shutdown and startup. Oxygen, hydrazine and copper
concentrations in the feedwater and copper concentrations of the steam will also
require special consideration, since the presence of oxidizing conditions increase the
release and transport of copper around the circuit.
water, as these can act synergistically and may initiate corrosion. For this reason, the
during boiler operation. The presence of oxygen also assists the transport of copper into
the steam, increasing the risk of deposition in the superheater and high pressure
turbine. It is also important to ensure that the pH, cation conductivity and chloride
concentration are within the limits given in the EPRI(1,3) guidelines for boiler water.
Hydrazine (or volatile reducing agents) should not be eliminated from plants with
mixed Fe-Cu feedwater heating systems.
Circuit Monitoring
6-28
the feedwater
copper


steam

copper
At full load, the normal EPRI guidelines values given in Figure 6-4 should be achieved.
parameters, sodium, cation conductivity and oxygen given in the EPRI(1,3) guidelines
steam, including copper. The normal operating levels, as given in the EPRI(1,3)
guidelines, should be achieved as soon as possible. These are given in Figure 6-4.
The road map, Figure 6-12, can be divided into 7 steps.
loaded units.
If the high purity feed and boiler water conditions can not be maintained during
units(1).
can be achieved by blowdown with drum units. However, compared with units with
all-ferrous feedwater heating systems described in Section 6.3, additional
considerations are required for units with mixed Fe-Cu feedwater heaters. To reduce
the risk of copper corrosion and transport, the ingress of oxygen must be minimized
6-29
and chemically reducing conditions must be maintained during all periods of

operation, shutdown and layup.
Step 1
No
Is system full?
Step 2
Yes
Step 4

low O2 scavenger?
(Section 4)
Step 3
Fill system per

AVT guidelines
Yes
No

Step 5

water per AVT
guidelines?
Step 5
Yes
Proceed with
startup
Fire to boiler
Step 5
Step 6

Monitor chemical
parameters
Step 6
Step 6


Step 7
and load
Figure 6-12 AVT - Startup of Drum Boilers with Mixed Metallurgy Feedwater
Heaters
For ease of reference, full details of the steps for the startup of drum units with mixed
Fe-Cu feedwater heating systems, operating on AVT, are given below:
6-30

for drum units operating on AVT(3).
then proceed.
Oxygen < 100 ppb
Iron < 100 ppb
Copper < 10 ppb
initially and silica may also be a problem. Achieving these limits is greatly facilitated
by using condensate polishing (See Section 3). When these limits are attained, the boiler
can be fired.
Step 6 - Monitoring
6-31
During startup, the concentration vs. pressure curves can be utilised to control sodium,
immediately by feeding trisodium phosphate or 1-2 ppm of sodium hydroxide.
Avoid excessive carryover of boiler water impurities into the steam. This includes
copper, whose transport can be minimized by avoiding ingress of oxygen and
maintaining chemically reducing conditions.
Step 7 - Full Load
Shutdown
pressurized, avoid air ingress to the feedheaters.
under nitrogen. Avoid air ingress to the feedwater heaters.
from high temperature (e.g. 130C) and maintain the boiler, superheaters and reheaters
dry. Continue as described under Layup.
6-32
During shutdown. if there is a leak in the reheaters, CO2 and, more importantly, flyash
A road map showing a scheme for shutdown of a drum boiler with a mixed Fe-Cufeedwater heating system operating with AVT is given in Figure 6-11. The time taken to
The road map for shutdown of a unit with a drum boiler operating on AVT with mixed
metallurgy feedwater heaters, Figure 6-11, can be divided into 5 steps.
treatment, except that higher purity water is required for units operating with AVT.
Unlike once-through boilers operating on AVT, described in Section 6.2, control of the
boiler water purity can be achieved by blowdown with drum boilers. However,
compared with units with all-ferrous feedwater heating systems described in Section
6.3, additional considerations are required for units with mixed Fe-Cu feedwater
heaters. To reduce the risk of copper corrosion and transport, the ingress of oxygen
must be minimized and chemically reducing conditions must be maintained.
Particular care should be exercised to prevent oxygen ingress during this period to
minimize pickup of copper. Blowdown should be maintained at an appropriate level to
remove contaminants from the system.
6-33
Step 2 - Outages
adjusted prior to shutdown, as indicated in the various options deliniated in Section 4.8
(Figure 4-8).
planned outage.
feedwater quality.
extent of the leak.
outlined above.
AVT(3).
6-34

include:
x
Polisher leakage
Poor regeneration

(orderly with polishers, immediate without polishers). The unit then requires careful
layup provisions.
6-35
Cycling and Peaking

Layup
Layup procedures are presented in Section 4, and a road map suitable for drum boilers
operating on AVT is depicted in Figure 4-8.
allow them to remain wet. Avoid air ingress to the feedwater heaters, as this leads to
the increased corrosion of copper alloys, particularly in the presence of ammonia.
Monitor oxygen and pH, and nitrogen and moisture, as appropriate. It is also possible
to store the boiler filled with a solution containing ammonia and hydrazine. Avoid
contact of solutions with high ammonia concentrations with the copper alloys.
6.5 REFERENCES
Institute, Palo Alto, Calif. EPRI CS-4629. June 1986
3. Cycle Chemistry Guidelines for Fossil Plants: All Volatile Treatment. Electric Power
4. G. M. W. Mann and R. Garnsey, Waterside Corrosion Associated with Two-Shift
Boiler Operation on All-Volatile Treatment Chemistry. Corrosion 79 Conference.
Materials Performance, October 1980, pp 32-38
5. State-of-Knowledge of Copper in Fossil Plant Cycles. Electric Power Research Institute,
6-36
7
OXYGENATED TREATMENT
7.1 INTRODUCTION
For the application of oxygenated treatment (OT) in units with once-through and drum
boilers, there are four indispensable prerequisites:
x
All-ferrous feedwater heater metallurgy (copper alloys may be used only in

condenser tubing).
Cation conductivity < 0.15 S/cm (at 25C) in condensate, feedwater, and steam.
Hydrazine and other oxygen scavengers are not used.
Condensate polishing
OT reduces or eliminates most of the typical AVT problems such as(1):

1. Flow-accelerated corrosion in the feedwater system and in the economizer inlet
tubes and headers.
2. Deposition of feedwater corrosion products on the boiler feed pump.
3. Corrosion product transport into the boiler resulting in orifice fouling, boiler
deposits and pressure drop problems, thermal fatigue boiler tube failures,
overheating boiler tube failures, and frequent chemical cleaning.
4. Turbine fouling.
5. Copper alloy condenser tube failures resulting from ammonia grooving (when
operating with OT at reduced ammonia levels).
Whereas the OT Guideline(1) covers in detail the transition from AVT to OT and normal
operation on OT, the following sections deal with startup and shutdown procedures,
cycling and peaking operation, and layup procedures for once-through and drum
boiler units operated on OT.
7-1

Oxygenated Treatment
7.2 ALL-FERROUS CYCLES WITH ONCE-THROUGH BOILERS

Current Normal Operating Guidelines
Oxygenated treatment (OT) uses high purity water to minimize corrosion and flowaccelerated corrosion (FAC) in the feedwater train. The normally desired cation
conductivity level in all plant cycle streams is <0.15 PS/cm (at 25qC); lower values are
preferred and attainable. OT can be applied only in plant cycles with all-ferrous
metallurgy and full-flow condensate polishing downstream of the condenser. With OT
for once-through units, an oxygen level of 30-150 ppb is maintained across the whole
plant cycle. The use of oxygen as a corrosion inhibitor allows satisfactory operation
over a large pH range (7-10). Thus, a marked reduction in plant cycle pH compared
with all-volatile treatment (AVT) is possible. The application of a pH range from 8.0 to
8.5 results in a reduction of condensate polisher regeneration frequency and the
associated costs.
During normal operation the vents on the deaerator are closed. It is also very
important with OT that the optimum heater vent position is maintained to ensure the
heater drains are fully protected from FAC. This usually involves the operator
ensuring that an oxidizing environment is present in the drains (ORP > 0mV)(8).
Figure 7-1 shows the cycle chemistry diagram of a cycle with a once-through boiler
operated on OT(1). Here, the normal target values and the action levels for condensate
pump discharge, combined condensate polisher effluent, economizer inlet, and steam
purity as well as for makeup treatment system effluent are provided.
Oxygenated treatment causes very stable conditions regarding the minimum corrosion
product transport in the plant cycle. A temporary oxygen or ammonia feed loss is not
considered to be a very serious situation. Efforts should be make to restore the feed of
both chemicals as soon as practical. Overfeed of ammonia and oxygen is likewise not a
serious event. However, if the condenser tubing is made of admiralty brass, then
ammonia overfeed could result in ammonia grooving. Again, efforts should be made
to establish the appropriate dosing as soon as practical. Particularly ammonia overfeed
does have cost consequences because of additional loading of the condensate polishers
when operated in the hydrogen-hydroxyl form.
7-2
Steam
Target
Sample
CR Sodium, ppb
12
> 12
CR Cation conductivity,
S/cma
0.15
0.2
0.3
> 0.65
Parameter

Target
Parameter
Air inleakage,
scfm/100 MWe

Target Sample
Parameter
a
8.0-8.5
CR Cation conductivity, S/cma
0.15
0.2
0.3
> 0.3
CR Oxygen, ppb
30-150
pH
LP
turbine
IP
turbine
HP
turbine
Sample
>1
Condensate
storage tank
Condenser
Makeup
treatment
system
Attemperation
Deaerator
Boiler
HP heaters
LP heaters
Condensate
polisher
Target
Sample
CR Sodium, ppb
S/cma
0.3
0.3
20
Parameter

Target

Parameter
Sample
CR Sodium, ppb
>3
>6
> 24
< 0.15
< 0.2
30-150
Base Load
Cycling
S/cma
1 (Action Level 1)
336 ( 2 weeks)
672 (4 weeks)
Oxygen, ppb
2 (Action Level 2)
48 (2 days)
96 (4 days)
3 (Action Level 3)
16
Immediate Shutdown
Targets
N (Normal)
Oxygen, ppb

= Continuous sample
= Chemical feed
Legend
Footnotes
Sample Frequency
Target Values
C = continuous
S = Grab. once per shift
W = grab. once per week
N = Normal
1 = Action Level 1
2 = Action Level 2
3 = Action Level 3
Figure 7-1 Cycle Chemistry Diagram of Once-Through Units on Oxygenated Treatment (core parameters only)
Startup Procedures
Startup is accomplished by essentially the same startup procedure as is used for AVT
(Section 6.2). Some minor variations in startup procedures exist, with the variation
depending upon the type of unit shutdown and subsequent layup procedure which
preceded the startup. For a short outage, no layup actions other than discontinuing
oxygen feed are recommended. For short duration layups, a relatively quick startup is
anticipated.
For longterm layups, increased levels of ammonia are suggested, and some additional
recirculation and venting are required to reduce ammonia levels and to reduce cation
conductivity to acceptable levels during startup. Normal station startup should be
performed as with AVT including ammonia addition but absolutely without hydrazine
or other oxygen scavenger addition. Startup should progress through cold and hot
cleanup, startup, and ramping activities as customary with AVT. Ammonia addition
begins with the first use of condensate polishers or when the condensate pumps are
started. Deaerator pegging and venting are performed until oxygen addition is started.
Oxygen addition does not begin until cation conductivity reaches 0.15 S/cm (at 25C)
and is continuing to downtrend. Deaerator vents should then be positioned as
customary in steady-state operation. The same is true for heater vents.
Once-through boilers utilize a by-pass system to facilitate cleanup of the pre-boiler
system during startup. This is a system of piping, valves and flash tank (vertical
separator) utilized during starting, stopping and low load operations. Firing a oncethrough boiler is not permitted unless minimum design limits for feedwater flow are
satisfied. Since once-through boilers have the flow going directly from the economizer
through the boiler to the turbine, the by-pass system provides protection of the turbine
during startup by isolating the turbine from the boiler by valves.
The by-pass system allows for circulation through the boiler, the feedwater heaters and
the waste cleanup (polishing) system to meet water quality requirements prior to firing.
Downstream of the flash tank, the by-pass system directs heater condensate and steam
to the deaerator and first point feedwater heater for heat recovery. Steam is supplied
from the flash tank for turbine cooling, loading and low load operation up to the oncethrough transfer load point. At the once-through transfer point, steam flow to the
turbine equals minimum boiler feedwater flow.
One of the most important advantages of OT is that startups can be accomplished much
faster than when the unit is operated with AVT. There should be no holds or other
ramping activities if the OT is operated in the optimum fashion according to the EPRI
guidelines(1). For startups following longterm layup, the feedwater iron levels should
7-4
Figure 7-2 shows a road map for startup of once-through units operating with OT.
Step 1: Startup preparation
Short-term
Startup
after short-term
or longterm
layup?
Longterm
Dry or wet
layup?
Dry
Is
system filled
for startup?
No
Fill or fill up with

deoxygenated
water (O2<10 ppb,
pH 8-8.5)
Wet
Fill system with

deoxygenated
water (O2<10 ppb,
pH >9)
Refill system with

deoxygenated
water (O2<10 ppb,
pH >9)
Yes
Step 2:
System
cleanup
Yes
Layup
duration
<4 weeks?
No
Commence startup.
Proceed with
available cleanup
loops; venting
very important
Commence startup
without any
cleanup actions except
venting
Is feedwater
cation conductivity
<0.65 S/cm?
Step 3: Fire to boiler
No
Yes
Fire to boiler.
Maintain temperature
ramp within boiler and
turbine manufacturers
requirements
Step 4: Transition to OT
Start oxygen dosing
and reduce pH to
8-8.5 if necessary
Yes
Is feedwater
cation conductivity
<0.15 S/cm?
No
Figure 7-2 Road map for the startup of once-through boilers operated with OT.
7-5
As mentioned above, the application of OT in all-ferrous cycles with once-through

boiler cycles markedly simplifies and shortens the startup procedure. For this reason,
the road map for startup of once-through units operating with OT (Figure 7-2) consists
of only 4 main steps.
Step 1 - Startup Preparation
Startup after short-term or longterm layup?
The first startup actions depend on the layup duration. In case of short-term or
intermediate layup, the procedure is simpler and faster compared to the case of a unit
which was the subject of a longterm layup.
Startup after short-term layup
Is system filled for startup?
Systems filled for startup can start up very fast without any cleanup actions except for
heater and deaerator venting. Otherwise the system has to be filled with deoxygenated
water (O2 < 10 ppb, pH 8-8.5). The cation conductivity of the water used for filling the
system should meet the EPRI OT Guideline. The startup after short-term layup is an
exception because it is, in contrary to startup after longterm layup, performed with a
feedwater pH of 8-8.5.
Startup after longterm layup
Dry or wet layup?
If the system has been stored dry it should be filled with deoxygenated water (O2 < 10
ppb, pH > 9) which meets the EPRI AVT guideline. If the system has been stored wet,
e.g. nitrogen cap combined with an oxygen free (< 10 ppb oxygen) ammonia treated
(pH > 9) water, it should be refilled with deoxygenated water (O2 < 10 ppb, pH > 9)
which meets EPRI AVT Guideline.
Layup duration < 4 weeks?
According to the general OT operation experience, it is possible to commence startup of
units stored for less than 4 weeks without any special cleanup actions except deaerator
and heater venting. In other cases, continue with available cleanup loops and take care
of adequate deaerator and heater venting.
7-6
Step 2 - System Cleanup

The startup of units operated with OT occurs without any oxygen dosing as in units
operated with AVT. The only difference to AVT is the feedwater pH of 8-8.5 in the case
of units starting up after short-term layup.
Is feedwater cation conductivity < 0.65 S/cm and downtrending?
If the feedwater cation conductivity is > 0.65 S/cm, then the by-pass of the pre-boiler
system (cleanup loop) has to be used to remove cycle contamination. Otherwise the
startup could begin without any cleanup actions.
An important part of this startup step is the deaerator and heater venting.
Step 3 - Fire to Boiler
It is required that the feedwater cation conductivity is < 0.65 S/cm and downtrending
prior to firing the boiler. Naturally, during startup the temperature ramp has to be
maintained within boiler and turbine manufacturers requirement.
The main cycle chemistry surveillance parameter in this and in the following startup
step is the feedwater cation conductivity. The other plan cycle core parameters
complete the information on the current cycle chemistry. Sampling and analysis for
corrosion products on a regular basis are, as a rule, not necessary. Nevertheless, it may
be meaningful to check the feedwater corrosion product level during some selected
starts to obtain more information on the required cleanup duration.
Step 4 - Transition to OT
Is feedwater cation conductivity < 0.15 S/cm?
The transition to OT (oxygen dosing and, if necessary, pH reduction to 8-8.5) takes
place only when the feedwater cation conductivity drops below 0.15 S/cm (at 25C).
Deaerator and heater vents should then be positioned as customary in steady-state
operation. Monitoring of all plant cycle core parameters is mandatory.
Shutdown Procedures
The procedures generally applicable to shutdown are included in Section 4.
Hydrazine or other oxygen scavengers should not be utilized in a unit operating on OT.
The preferred practice is to stop the oxygen feed at least one hour before shutdown
and, for longterm shutdowns, in addition, to increase the pH in the cycle. Oxygen and
7-7
ammonia addition must be stopped for all types of shutdown. In order to exclude the
possibility of oxygen in-leakage into the shutdown unit by way of leaking valves, a
physical disconnection of the oxygen supply from the oxygen dosing line is advised.
The checklist for securing sample flows and on-line analyzers should be gone through
point by point.
Short-Term Shutdown.
Figure 7-3 graphically depicts guidance for short-term shutdown(1). The guidance
consists simply of stopping oxygen feed at least one hour before shutdown of the unit.
Deaerator vents should be opened, if they are not normally open, or the deaerator
venting should be increased to aid in cycle deaeration in conjunction with stopping the
oxygen feed. At the same time, the low pressure and high pressure heaters should be
carefully vented. Shutdown of ammonia feed should occur simultaneously with unit
shutdown.
Operation
pH
1 hour
Shutdown
8-8.5
NH3
30-150 ppb
O2
(injected)
Cation
conductivity
0 ppb
<0.15 S/cm
Figure 7-3 Shutdown and Operation Guidance for OT Chemistry for Short-Term
Shutdowns
7-8
Longterm Shutdown.
Figure 7-4 graphically depicts guidance for longterm shutdown. The guidance consists
of stopping oxygen feed at least one hour before shutdown of the unit and of increasing
ammonia feed rates. Simultaneously, the deaerator vents should be opened, if they are
not normally open, or the deaerator venting should be increased to aid in cycle
deaeration in conjunction with stopping the oxygen feed. At the same time, the low
pressure and high pressure heaters should be carefully vented. The object of the
increased ammonia feed rates is to achieve a pH higher than 9.0.
Then, both the oxygen level in the whole cycle and the cycle pH are comparable with
those typical for AVT (feedwater oxygen <10 ppb and pH >9.0). During the longterm
shutdown, the cycle can be regarded and treated as a cycle operated on AVT (2) (see
Section 6.2). The only exception is the already mentioned elimination of hydrazine or
other oxygen scavenger dosing even for a wet layup.
Operation
1 hour
Shutdown*
>9.0
pH
8-8.5
NH3
30-150 ppb
O2 (injected)
0 ppb
0.2 S/cm
Cation conductivity
<0.15 S/cm
Figure 7-4 Shutdown and Operation Guidance for OT Chemistry for Long-Term Shutdowns.
Note *: Dependent on wet or dry storage and utilization of nitrogen blanketing (See Section 4)
7-9
Emergency Shutdown.
In case of an emergency shutdown for reasons of a technical fault (e.g., defects in the
electrical equipment, a boiler tube failure), the unit is shut down with the optimum
operating chemistry. If it is foreseeable that the unit will be brought back into service
very fast (e.g., overnight or over a weekend), additional chemical measures are
unnecessary. In case the shutdown will continue for a longer period of time (e.g.,
several days or longer), the replacement of oxygen-containing water with an oxygenfree (<10 ppb oxygen) ammonia treated (pH >9) water makes sense. Customary layup
procedures have to be employed for prolonged shutdowns.
Shutdown as a Result of a Serious Chemistry Excursion.
Condenser cooling water in-leakage, makeup water contamination, condensate storage
tank contamination or improper condensate polisher regeneration can lead to a
dangerous increase in cation conductivity or sodium or silica content. With OT, a
cation conductivity excursion is the most serious of chemical transients and must be
dealt with very seriously and promptly. In case of an increasing cation conductivity,
the following actions are possible:
Cation Conductivity
PS/cm (at 25qC)
<0.15
>0.2 and <0.3
>0.3
>2.0 for 5 minutes or
>5.0 for 2 minutes
Action Required
Normal operating value, continue normal operation.
Increase system pH to AVT level (9.2-9.6).
Stop oxygen feed; operate on AVT without the use of
hydrazine or other oxygen scavengers.
Stop firing.
After a shutdown forced by a cation conductivity excursion, a unit drain and cleanup
using a non-contaminated water treated in accordance with the AVT requirements is
recommended(2). With this, the standard cleanup loops including condensate polisher
(if the polisher is not the source of contamination) can be employed.
Cycling and Peaking Operation(3-7)

During cycling and peaking operation, as well as a consequence of a sliding pressure
operation, cation conductivity excursions, oxygen content variations, and pH
excursions may occur. The actions required for cation conductivity excursions are
discussed in the section Shutdown Procedures.
Particularly during peaking operation, longer periods with slightly higher cation
conductivity than the steady-state normal operating value (i.e., >0.15 PS/cm) are not an
exceptional case. In many cases, even a cation conductivity of <0.3 PS/cm (at 25qC)
7-10
cannot be reached because of the relatively short duration of the operating period; then
the unit can be operated only on AVT. There is a risk that such a unit could sooner or
later lose its passivation. In such cases, a longer steady-state operation with a renewed
cycle passivation has been proven as the best remedy for reestablishing low corrosion
product transport throughout the cycle.
In many units the oxygen and ammonia feed are not automatically controlled. As a
result of load fluctuations both the oxygen content and the pH may vary considerably.
It is recommended to set the manually adjusted dosing to a lower value within the
recommended range for oxygen content (30 ppb) and pH (8.0) during full load
operation to preclude unnecessary overdosing in low load periods.
Layup Practices
Section 4, Shutdown and Layup Considerations Common to Most Units describes the
general information on layup practices for all types of chemistry.
An OT specific variant of wet layup for once-through boilers is the short-term layup
with optimum operating chemistry after an emergency shutdown. If it is foreseeable
that the unit will be brought back into service very fast (e.g., overnight or over a
weekend), additional chemical measures are unnecessary. In case the shutdown will
continue for a longer period of time, additional chemical measures are indispensable.
As an alternative to the usual replacement of oxygen containing system contents with
oxygen free (< 10 ppb oxygen) ammonia treated (pH > 9) water, keeping the optimum
operating chemistry even during layup makes sense. With this alternative, a frequent
change or a continuous rinsing of the system contents with an oxygen containing (30150 ppb oxygen) ammonia treated (pH 8.0-8.5) water has proved to be worthwhile.
The sense of such measures is to ensure that the optimum redox conditions are kept in
the system even during the idle period. Naturally, the cation conductivity must not
exceed 0.3 S/cm (at 25C).
For a longterm layup both dry layup and a nitrogen cap combined with an oxygen free
(< 10 ppb oxygen) ammonia treated (pH > 9) water within the system are practicable.
Keeping a flow of oxygenated water through the boiler is also possible but in most
cases not economical.
Because OT represents the best available treatment for all-ferrous systems with oncethrough steam generators, a proper layup of a unit operated with OT is very important
particularly in the case of prolonged idle periods. The cycle parts at most risk are the
steam and feedwater side of the LP and HP heaters (including drains and vents), the
superheaters and reheaters, and the LP turbine. These cycle components should always
be included in the planned layup measures. See Discussion in Section 4.
7-11
7.3 ALL-FERROUS CYCLES WITH DRUM BOILERS

Current Normal Operating Guidelines
The use of OT for drum units is very similar to that of for once-through units described
in the previous sub-section. Oxygenated treatment (OT) uses high purity water to
minimize corrosion and flow-accelerated corrosion (FAC) in the feedwater train. The
normally desired cation conductivity level in feedwater and steam is < 0.15 S/cm (at
25C) whereas in the boiler water it is < 1.5 S/cm (at 25C); lower values are preferred
and attainable. OT can be applied only in plant cycles with all-ferrous feedwater
metallurgy and full-flow condensate polishing downstream of the condenser. With OT
for drum units, an oxygen level of 30-50 ppb is maintained in feedwater and steam.
The application of a pH range from 9.0-9.5 enables a slight possible reduction of
condensate polisher regeneration frequency. Since a contaminant concentration in
boiler water (downcomer) is conceivable even with the best feedwater, the oxygen level
at the drum boiler downcomer is limited to < 10 ppb.
During normal operation the vents on the deaerator are closed. It is also very
important with OT that the optimum heater vent position is maintained to ensure the
heater drains are fully protected from FAC. This usually involves the operator
ensuring that an oxidizing environment is present in the drains (ORP > 0mV)(8).
Figure 7-5(1) shows the cycle chemistry diagram of a cycle with a drum boiler operated
on OT. Here, the normal target values and the action levels for condensate pump
discharge, combined condensate polisher effluent, economizer inlet, boiler water
(downcomer), and steam as well as for makeup treatment system effluent are provided.
7-12
Steam
Target
Parameter
Sample
CR Sodium, ppb
>3
>6
> 12
S/cma
0.15
> 0.2
> 0.3

Target
Parameter
Air inleakage,
scfm/100 MWe
Boiler Water (Downcomer)

Target Sample
Parameter
pH

Oxygen, ppb
Immediate
Shutdown
< 8.5
> 9.2
< 7.5
< 3.0
< 5.0
8.5-9.2
1.5
> 10
HP
turbine
>1
Makeup
treatment
system
Deaerator
Boiler
Target Sample
9.0-9.6
< 9.0
> 9.6
0.15
CR Oxygen, ppb
30-50
pH
Condensate
storage tank
Attemperation
Blowdown
Boiler
water
LP
turbine
Condenser
Economizer Inlet
Parameter
IP
turbine
Sample
> 0.2
> 0.3
> 0.65
HP heaters
LP heaters
Condensate
polisher
Combined Condensate Polisher Effluent

Parameter
CR Sodium, ppb

N (Normal)
Base Load
Cycling
1 (Action Level 1)
336 ( 2 weeks)
672 (4 weeks)
2 (Action Level 2)
48 (2 days)
96 (4 days)
3 (Action Level 3)
16
Immediate Shutdown

Oxygen, ppb
Legend
Sample
>3
6
>6
12
> 24
< 0.15
> 0.2
30-50
Footnotes
Sample Frequency
Target Values
C = continuous
S = Grab. once per shift
W = grab. once per week
N = Normal
1 = Action Level 1
2 = Action Level 2
3 = Action Level 3
Sample
S/cma
0.3
> 0.3
20
Oxygen, ppb
Target

Targets
Target
Parameter
CR Sodium, ppb

c = Dependent upon economizer inlet/downcomer oxygen
Figure 7-5 Cycle Chemistry Diagram of Drum Units on Oxygenated Treatment (OT)

= Continuous sample
= Chemical feed
Oxygenated treatment causes very stable conditions regarding the minimum corrosion
product transport in a plant cycle. A temporary oxygen feed loss is not considered to
be a very serious situation. Efforts should be made to restore the feed of oxygen as
soon as practical. A temporary ammonia feed loss could result in an undesirable boiler
water pH reduction. Efforts should be made to restore the feed of ammonia as soon as
possible. Overfeed of ammonia is likewise not a serious event. Again, efforts should
be made to establish the appropriate dosing as soon as practical. The ammonia
overfeed does have cost consequences because of additional loading of the condensate
polishers when operated in hydrogen-hydroxyl form. An overfeed of oxygen could
endanger the waterwalls when contamination is present, and for that reason, has to be
precluded by means of appropriate technical measures.
Startup Procedures
Startup is accomplished using essentially the same startup procedure as used for AVT
(Section 6.3). Some minor variations in startup procedures exist, with the variation
depending upon the type of unit shutdown and subsequent layup procedure which
preceded the startup. Since for a short outage, no layup actions other than
discontinuing oxygen feed are recommended, a relatively quick startup is anticipated.
For longterm layups, in which increased levels of ammonia are used, some additional
recirculation and venting are required to reduce ammonia levels and to reduce cation
conductivity to acceptable levels. Normal station startup should be performed as with
AVT including ammonia but absolutely without hydrazine or other oxygen scavenger
addition. Startup should progress through cold and hot cleanup, startup, and ramping
activities as customary with AVT. Ammonia addition begins with the first use of
condensate polishers. Deaerator pegging and venting are performed until oxygen
addition is started. The blowdown is used to reduce the boiler water cation
conductivity.
Oxygen addition does not begin until feedwater cation conductivity reaches 0.15
S/cm (at 25C) and is continuing to downtrend and until the boiler water
(downcomer) cation conductivity has reached < 1.5 S/cm (at 25C). Deaerator vents
should then be positioned as customary in steady-state operation. The same is true for
heater vents.
One of the most important advantages of OT is that startups can be accomplished much
faster than when the unit is operated with AVT. For startups following short-term
layup, there should be no holds or other ramping activities if the OT is operated in the
optimum fashion according to the EPRI guidelines(1). For startups following longterm
layup, the feedwater iron levels still should not be a critical parameter. Here the main
monitoring parameters are economizer inlet cation conductivity, oxygen, and pH (by
7-14
means of specific conductivity) as well as boiler water cation conductivity, oxygen, and
pH.
loaded units.
Figure 7-6 shows a road map for startup of drum-type units operating with OT.
7-15
Step 1: Startup preparation
Startup
after short-term
or longterm
layup?
Short-term
Longterm
Dry or wet
layup?
Dry
Is
system filled
for startup?
Fill or fill up with

deoxygenated
water (O2<10 ppb,
pH >9)
No
Wet
Fill system with

deoxygenated
water (O2<10 ppb,
pH >9)
Refill system with

deoxygenated
water (O2<10 ppb,
pH >9)
Yes
Step 2:
System
cleanup
Yes
Layup
duration
<4 weeks?
No
Commence startup.
Proceed with
available cleanup
loops; venting
very important
Commence startup
without any
cleanup actions except
venting
Is feedwater
cation conductivity
<0.65 S/cm?
Step 3: Fire to boiler
No
Yes
Fire to boiler.
Maintain temperature
ramp within boiler and
turbine manufacturers
requirements
Increase blowdown
No
Step 4:
Transition
to OT
No
No
Start oxygen
dosing and reduce
blowdown
Is feedwater
cation conductivity
<0.15 S/cm?
Is the boiler
load higher than
minimum OT
load?
Yes
Is boiler water
cation conductivity
<1.5 S/cm?
Yes
Yes
Figure 7-6 Road map for the startup of drum boilers operated with OT.
7-16
The application of OT in all-ferrous cycles with drum-type boilers markedly simplifies

and shortens the startup procedure over that for AVT. For this reason, the road map
for startup of drum-type units operating with OT (Figure 7-6) consists of only 4 main
steps.
Step 1 - Startup Preparation
Startup after short-term or longterm layup?
The first startup actions depend on the layup duration. In case of short-term or
intermediate layup, the procedures are simpler and faster than in the case of a unit
which was the subject of a longterm layup.
Startup after short-term layup
Is system filled for startup?
Systems filled for startup can start up very fast, without any cleanup actions except for
heater and deaerator venting. Otherwise the system has to be filled with deoxygenated
water (O2 < 10 ppb, pH > 9). The cation conductivity of the water used for system
filling should meet the EPRI AVT Guideline (2).
Startup after longterm layup
Dry or wet layup?
If the system has been stored dry, it should be filled with deoxygenated water (O2 < 10
ppb, pH > 9) which meets the EPRI AVT guideline. If the system has been stored wet,
e.g. nitrogen cap combined with an oxygen free (< 10 ppb oxygen) ammonia treated
(pH > 9) water, it should be refilled with deoxygenated water (O2 < 10 ppb, pH > 9)
which meets EPRI AVT Guideline.
Layup duration < 4 weeks?
According to the general OT operation experience, it is possible to commence startup of
units stored for less than 4 weeks without any special clean-up actions except deaerator
and heater venting. In other cases, continue with available cleanup loops and take care
of adequate deaerator and heater venting.
Step 2 - System Cleanup
The startup of units operated with OT occurs without any oxygen dosing, as with AVT.
7-17
If feedwater cation conductivity is > 0.65 S/cm, the by-pass of the pre-boiler system
(cleanup loops) can be used to remove cycle contamination (if a by-pass is available).
Otherwise the startup could begin without any cleanup actions. An important part of
this startup step is the deaerator and heater venting.
Step 3 - Fire to Boiler
It is required that the feedwater cation conductivity reaches < 0.65 S/cm and tends to
downtrend prior to firing the boiler. Naturally, during startup the temperature ramp
has to be maintained within boiler and turbine manufacturers requirement.
The main cycle chemistry surveillance parameter in this and in the following startup
step is the feedwater cation conductivity and pH as well as boiler water cation
conductivity and pH. The other plant cycle core parameters complete the information
on the current cycle chemistry. Sampling and analysis for corrosion products on a
regular basis are, as a rule, not necessary. Nevertheless, it may be meaningful to check
the feedwater corrosion product level during some selected starts to get more
information on the required cleanup duration.
Step 4 - Transition to OT
A feedwater cation conductivity below 0.15 S/cm (at 25C) is the first precondition for
the transition to OT. Deaerator and heater vents should then be positioned as
customary in steady-state operation.
Is boiler water conductivity < 1.5 S/cm?
Reaching this value is the second precondition for the transition to OT. In case of need,
the blowdown is used to reduce the boiler water cation conductivity.
Is the boiler load higher than minimum OT load?
The transition to OT is possible only if the boiler load reaches the unit-specific
minimum OT load. See EPRI Guidelines (1) for information on establishing the oxygen
recirculation ratio and the minimum load acceptable for oxygen addition. This is the
last precondition before the transition to OT. Otherwise, the unit has to continue
operation with AVT.
Start oxygen dosing.
Only when the three above mentioned preconditions are fulfilled (feedwater cation
conductivity < 0.15 S/cm, boiler water cation conductivity < 1.5 S/cm, and boiler
7-18
load higher than minimum OT load), is oxygen dosing permitted. If possible, the
blowdown can be reduced. Deaerator and heater vents should then be positioned as
customary in steady-state operation.
Monitoring of all plant cycle core parameters is important and indispensable during
Step 4.
Shutdown Procedures
The procedures generally applicable to shutdown are included in Section 4.
Hydrazine and other oxygen scavengers should not be utilized in a unit operating on
OT. The preferred practice is to stop the oxygen feed at least one hour before
shutdown and, for longterm shutdowns, in addition, to increase the pH in the cycle.
The maximum tolerable pH value depends on the condenser metallurgy. If the
condenser tubing is made of admiralty brass, then a higher pH could result in ammonia
grooving. Oxygen and ammonia addition must be stopped for all types of shutdown.
In order to exclude the possibility of oxygen in-leakage into the shutdown unit by way
of leaking valves, a physical disconnection of the oxygen supply from the oxygen
dosing line is advised. The checklist for securing sample flows and on-line analyzers
should be gone through point by point.
Short-Term Shutdown.
(1)
Figure 7-7 graphically depicts guidance for short-term shutdown . The guidance
consists simply of stopping oxygen feed at least one hour before shutdown of the unit.
Deaerator vents should be opened, if they are not normally open, or the deaerator
venting should be increased to aid in cycle deaeration in conjunction with stopping
oxygen feed. At the same time, the low pressure and high pressure heaters should be
carefully vented. Shutdown of ammonia feed should occur simultaneously with unit
shutdown.
7-19
Low Power
Operation
High Power
Operation
Shutdown
>9.0
9-9.6
Feedwater pH
1 hour
Minimum
OT load
Feedwater NH3
Feedwater O2
(injected)
Feedwater
cation conductivity
Downcomer
cation conductivity
Downcomer oxygen
residual (downcomer)
30-50 ppb
0 ppb
0 ppb
<0.15 S/cm
<1.5 S/cm
10.0 ppb
Figure 7-7 Operation and Shutdown Guidance for OT Chemistry for Short-term
Shutdowns (Drum Boiler Unit)
Longterm Shutdown.
Figure 7-8 graphically depicts guidance for longterm shutdown. The guidance consists
of stopping oxygen feed at least one hour before shutdown of the unit and of increasing
ammonia feed rates. Simultaneously, the deaerator vents should be opened, if they are
not normally open, or the deaerator venting should be increased to aid in cycle
deaeration in conjunction with stopping the oxygen feed. At the same time, the low
pressure and high pressure heaters should be carefully vented. The object of the
increased ammonia feed rate is to achieve a pH higher than 9.0.
7-20
Low Power
Operation
High Power
Operation
9-9.6
1 hour
Shutdown
>9.0
Feedwater pH
Minimum OT load
Feedwater NH3
Feedwater O2
(injected)
30-50 ppb
0 ppb
0 ppb
Feedwater
cation conductivity
<0.15 S/cm
Downcomer
cation conductivity
<1.5 S/cm
Downcomer oxygen
residual (downcomer)
10.0 ppb
Figure 7-8 Operation and Shutdown for OT Chemistry for Longterm Shutdowns
(Drum Boiler Unit)
Then, both the oxygen level in the whole cycle and the cycle pH are comparable with
those typical for AVT (feedwater oxygen < 10 ppb and pH > 9.0). During the longterm
shutdown, the cycle can be regarded and treated as a cycle operated on AVT(2). The
only exception is the already mentioned elimination of the hydrazine or other oxygen
scavenger dosing even for a wet layup.
Emergency Shutdown.
In case of an emergency shutdown for reasons of a technical fault (e.g., defects in the
electrical equipment, a boiler tube failure), the unit is shutdown with the optimum
operating chemistry. If it is foreseeable that the unit will be brought back into service
very fast (e.g., overnight or over a weekend), additional chemical measures are
unnecessary. In case the shutdown will continue for a longer period of time (e.g.,
7-21
several days or longer), the replacement of oxygen containing water with an oxygen
free (< 10 ppb oxygen) ammonia treated water (pH > 9) makes sense. Customary layup
procedures have to be employed for prolonged shutdowns.
Shutdown as a Result of a Serious Chemistry Excursion.
Condenser cooling water in-leakage, makeup water contamination, condensate storage
tank contamination, or improper condensate polisher regeneration can lead to a
dangerous increase in cation conductivity or sodium or silica content. With OT, a
cation conductivity excursion is the most serious of chemical transients and must be
dealt with very seriously and promptly. In case of an increasing cation conductivity,
the following actions are possible:
Feedwater Cation
Conductivity
PS/cm (at 25qC)
Action Required
<0.15
Normal operating value, continue normal operation.
>0.2 and <0.3
Increase system pH to AVT level (9.2-9.6).
>0.3
Stop oxygen feed; operate on AVT without the use of

hydrazine or other oxygen scavengers.
Other chemical transients (e.g. sodium and silica) must be dealt with in the same way
as with AVT.
A boiler water cation conductivity excursion is also a serious chemical transient and
must be dealt with very seriously and promptly. In case of an increasing boiler water
(downcomer) cation conductivity, the following actions are possible.
Boiler Water Cation
Conductivity
PS/cm (at 25qC)
Action Required
<1.5
Normal operating value (preferably <1.0), continue normal

operation.
1.5 -3.0
Increase boiler blowdown
>3.0
Stop oxygen feed; increase feedwater pH to AVT level (9.29.6). Do not use hydrazine or other oxygen scavengers.
Follow the AVT Guideline(2).
7-22
Cycling and Peaking Operation

During cycling and peaking operation, as well as a consequence of a sliding pressure
operation, cation conductivity excursions, oxygen content variations, and pH
excursions may occur. The actions required for cation conductivity excursions are
discussed under Shutdown Procedures.
Particularly during peaking operation longer periods with slightly higher feedwater
cation conductivity than the steady-state normal operating value (i.e., < 0.15 S/cm at
25C) are not an exceptional case. In many cases, even a feedwater cation conductivity
of < 0.3 S/cm (at 25C) cannot be reached because of the relatively short duration of
the operating period; then the unit can be operated only on AVT. There is a risk that
such a unit could sooner or later lose its passivation. In such cases, a longer steadystate operation with a renewed cycle passivation has been proven as the best remedy
for reestablishing low corrosion product transport throughout the cycle.
During the conversion to OT, the oxygen recirculation ratio and a minimum load
(1)
acceptable for oxygen addition should have been selected . If the boiler is operated at
a lower load than the selected minimum OT load, the oxygen feed should be shut off.
Layup Practices
Section 4, Shutdown and Layup Considerations Common to Most Units describes the
general information on layup practices for all types of chemistry.
An OT specific variant of wet layup for drum boilers is the short-term layup with
optimum operating chemistry after an emergency shutdown. If it is foreseeable that the
unit will be brought back into service very fast (e.g., overnight or over a weekend),
additional chemical measures are unnecessary. In case the shutdown will continue for
a longer period of time, additional measures are indispensable.
For a longterm layup both dry layup and a nitrogen cap combined with an oxygen free
(< 10 ppb oxygen) ammonia treated (pH >9) water within the system are practicable.
OT represents one of the best available treatments for all-ferrous systems with drum
boilers. Nevertheless, a proper layup of such a unit operated with OT is very
important particularly in case of prolonged idle periods. The cycle parts at most risk
are the steam and feedwater side of the LP and HP heaters (including drains and
vents), the waterwalls and the drum, the superheaters and reheaters, and the LP
turbine. All mentioned cycle components should always be included in the planned
layup measures. See discussion in Section 4.
7-23
7.4 REFERENCES
1. Cycle Chemistry Guidelines for Fossil Plants: Oxygenated Treatment. EPRI TR-102285,
Dec. 1994.
2. Cycle Chemistry Guidelines for Fossil Plants: All-Volatile Treatment. EPRI TR-105041,
April 1996.
3. A. H. Rudd, J. M. Tanzosh, Developments Applicable to Improved Coal-Fired Power
Plants, Nov 19-21, 1986. Electric Power Research Institute, Palo Alto, Calif. USA.
4. Babcock & Wilcox 7A-1K32, Nov. 1995. Operating Instructions for Universal Pressure
Boilers. Babcock & Wilcox-A McDermott Co., 20 South Van Buren, Barberton, Ohio
USA.
5. Babcock & Wilcox 7A-1, 1-K32 (FPG) Aug 9, 1982. Initial Waterside Clean-up
Universal Pressure Boilers (Boilers with Integral Primary Superheaters), Babcock &
Wilcox-A McDermott Co., 20 South Van Buren, Barberton, Ohio, USA.
6. A. H. Rudd, Variable Pressure Boiler Operation, Canadian Electrical Association, Sept.
18-20, 1972, Calgary, Alberta, Canada BR-978 PGTP 72-53. Babcock & Wilcox-A
McDermott Co., 20 South Van Buren Avenue, Barberton, Ohio, USA.
7. Combustion Fossil Power, Published by Combustion Engineering, Windsor Locks,
Connecticut, 1991, 4th Edition Chapter 7, Central Station Steam Generators.
8. R. B. Dooley and J. Matthews. The Current State of Cycle Chemistry for Fossil
Plants. Fifth International Conference on Fossil Plant Cycle Chemistry. Proceedings
Ed. By R. B. Dooley and J. Matthews. EPRI TR-108459, November 1997.
7-24
8
CAUSTIC TREATMENT FOR DRUM BOILERS
8.1 INTRODUCTION
With the traditional form of all-volatile treatment, ammonia and hydrazine are
added to the feedwater to provide chemical conditions that protect the feedwater
heaters, boiler, superheater, reheater and turbine against corrosion, without further
chemical additions.
(1)
All-volatile treatment can also be used for drum-type boilers , provided high purity
feedwater is available and the build-up of impurities in the boiler water is strictly
protection against corrosion, but also reduces the risk of carrying over boiler water salts
conditions can not be maintained during startup, operation and shutdown, it may be
necessary to adopt another form of chemical conditioning, such as phosphate (see
section 5) or caustic treatment, as discussed below.
Preliminary guidance on the use of caustic treatment of boiler water was published in
an EPRI(2) report on Sodium Hydroxide for Conditioning the Boiler Water of DrumType Boilers in 1995. Cycle diagrams were provided for drum-type boilers with all
ferrous and mixed Fe-Cu metallurgy feedwater heating systems. Only high pressure
drum boilers with reheat were considered and EPRI interim guidance with the normal
limits and three action levels and core parameters were proposed for 2500 psi (17
MPa) coal fired drum-type boilers. Guidance was included on the application,
experience, benefits, limitations and implementation of caustic treatment.
Further considerations of caustic treatment were included in the EPRI report on
Selection and Optimization of Boiler Water and Feedwater Treatment of Fossil Plants(3).
In general, the features for the feedwater and steam for all-volatile treatment (AVT) for
drum boilers, also apply to caustic treatment (CT). However, these need to be
supplemented by additional considerations for the boiler water. Some units with drum
8-1

Caustic Treatment for Drum Boilers
boilers may be equipped with a condensate polisher, but many units are not and,
therefore, will be more susceptible to the effects of condenser leaks.
Caustic treatment can be used for drum boilers with all-ferrous and mixed metallurgy
feedwater heating systems. As with phosphate treatment, adding sodium hydroxide as
a solid alkalizing agent to the boiler water, increases the tolerance of the boiler to
ingress of corrosive contaminants, such as chloride. However, if present in too high a
concentration, it can lead to caustic gouging and increased boiler corrosion. In addition,
special care has to be taken to prevent carryover of boiler water into the steam, as the
presence of sodium hydroxide in water droplets could lead to stress corrosion cracking
of austenitic components, such as superheaters and turbines.
Many of the features discussed in Section 6 on All-Volatile Treatment also apply to
Caustic Treatment, with the proviso that particular care has to be taken in controlling
the concentration of sodium hydroxide in the boiler water and carry over into the
steam. In order to avoid too much repetition, the reader is referred to the appropriate
parts of the AVT guidance, Section 6.3 for All-Ferrous Feedwater Heating Systems and
Section 6.4 for Mixed Metallurgy Feedwater Heating Systems. This Section 8 of the
guidelines will concentrate on the additional considerations for Caustic treatment.
8.2 ALL-FERROUS FEEDWATER HEATING SYSTEMS

Current Guidance Document
The current guidance on caustic treatment (CT) for drum boilers with all-ferrous
feedwater heating systems is given in Figure 8-1 for reheat plants, including the core
parameters. The normal limits and three action levels for sodium, chloride, sulfate,
silica and cation conductivity in boiler water are given in the EPRI (2) report on Sodium
Hydroxide Conditioning the Boiler Water of Drum-Type Boilers. Non-reheat plants
were not considered in the report.
Startup
The basic considerations outlined in Section 6.3 for AVT apply during startup for
Caustic Treatment, with the addition that special care has to be taken to prevent any
carryover of sodium hydroxide in the boiler water, as this could lead to stress corrosion
of austenitic components in the steam circuit.
Section 3 explains how the action levels can be utilized during unit startup. The
cumulative operating hours per year for which the various action levels can be
exceeded are twice the values for cycling units, as compared to base loaded units. No
chemistry pressure curves were developed for Caustic Treatment, but the target values
given in Figure 8-1 should be achieved.
8-2
Reheat Steam
Target
Parameter
Saturated Steam
Sample
CR Sodium, ppb
0.3
Silica, ppb
C or S
Chloride, ppb
>5
> 10
> 0.55
>1.0
>2
>3
10
>10
> 20
> 40
C or S
>2
>5
>10
Sulfate, ppb
>2
>5
>10
100
>100
Target
Parameter
Air inleakage,
scfm/100 MWe
Injection
Dosage
Target
Parameter
Hydrazine, ppb
< 20
Sample
>1
Target
N
Sample
Parameter
CR Sodium
Silica
10

Boiler Water
Target
Target
Parameter
Immediate
Shutdown
>3
0.4 > 0.4 > 0.8 >1.2
0.5> 0.5. >1.0 >1.5
Sample
C or S 1.2 >1.2 > 2
Sodium, ppm
Chloride, ppm
Sulfate, ppm
Silica, ppm
9.4 < 9.4 < 9.3 < 9.2

9.6 > 9.6 > 9.7 > 9.6
<8
Specific conductivity, S/cma

< 8 > 8 >15 > 25
< 1.0 < 0.8 < 0.6

C or S 1.01.5 >1.5 > 2.0 > 3.0
NaOH, ppm (min 2.5 x Cl)
C or S
Ammonia
LP
turbine
IP
turbine
HP
turbine
Sample
Target
Condensate
storage tank
Attemperation
Blowdown
Makeup
treatment
system
Deaerator
Parameter
Condenser
> 10
6-12 >12 > 20 > 30

C
Phosphate
or NaOH
C or S 0.2 > 0.2 > 0.4 > 0.7
CR pHa
Parameter
or sodium
Sample
Sodium, ppb
Chloride, ppb
Sulfate, ppb
C or D
D
5
3
3
Silica, ppb
Target
Sample
9.2-9.6
8.8-9.1
< 9.2
> 9.6
< 8.8
> 9.1
pHa
0.2
0.45
0.85
> 0.85
Iron, ppb
>5
Copper, ppb
1-10
>2
15
20
> 20
10
20
> 20
CR Oxygen, ppb All ferrous

Mixed Fe-Cu
Oxygen, ppb
Sample
10
Deaerator Inlet
Parameter
Hydrazine, ppb
Sample
< 20
N (aluminum
tanks only)
10
Target
Sample
Target
Parameter
>5
>10
> 20
0.2
> 0.2
10
>10
10
>10
> 20
Plants without
polisher
>5
>10
0.3
> 0.3
Plants without
polisher
0.2
> 0.2
> 0.36
> 0.65
200
> 200
Oxygen, ppb
20
> 20
> 40
S/cma
Plants with
polisher
CR S/cma
Sample
Plants with
polisher
CR Sodium, ppb
CR Sodium, ppb
Silica, ppb

Sodium, ppb

Parameter
Target
Condensate
polisher
Ammonia
and
hydrazine
Target
Parameter
300
100
Sample
Target
Deaerator Outlet
Consistent with pH
W
C
Parameter
Parameter
0.1
LP heaters
HP heaters
10
Oxygen
Boiler
S/cma

Targets
N (Normal)
Base Load
Cycling
1 (Action Level 1)
336 ( 2 weeks)
672 (4 weeks)
2 (Action Level 2)
48 (2 days)
96 (4 days)
3 (Action Level 3)
16
Immediate Shutdown
Footnotes
Legend
Sample Frequency
Target Values
C = continuous
N = Normal
1 = Action Level 1
2 = Action Level 2
3 = Action Level 3

b = See curves of maximum allowable concentration
versus pressure
c = Target values may be adjusted to reflect capabilities
of installed equipment

= Core parameter
= Continuous sample
= Chemical feed
Figure 8-1 Cycle Chemistry Diagram for Drum Type Coal-Fired Boiler on Sodium Hydroxide Treatment (Plants with
Reheat)
As mentioned previously, special care has to be taken to avoid excessively high

concentrations of sodium hydroxide in the boiler water, and carryover of sodium
hydroxide into the steam. This can be prevented by carefully monitoring sodium in
steam. The steps used during startup will be plant specific and, depending on the
practicality, the following stages should be monitored, at least during a trial period:
Circuit Monitoring
a) Addition of hydrazine (if used)and

pH, NaOH or specific conductivity, cation

conductivity, chloride, and corrosion
products

steam
At full load, the values given in the EPRI guidance document(2) should be achieved.
parameters are within the EPRI action levels 1-3, see Figure 8-1. The core parameters,
sodium, cation conductivity and oxygen given in the EPRI guidance document(2) should
be monitored at the condensate pump discharge, condensate polisher outlet (if
installed), economizer inlet, boiler water (preferably at downcomer), including pH and
specific conductivity or NaOH, and steam. The normal operating levels, as given in the
EPRI guidance document(2), should be achieved as soon as possible. These are given in
Figure 8-1.
feedwater heating system operating with CT is given in Figure 8-2. The time taken to
startup, it may be necessary to adopt another form of chemical conditioning, such as
phosphate. The Selection and Optimization document provides advice and guidance on
the optimum boiler water and feedwater choices for drum units(3). The road map,
Figure 8-2, can be divided into 7 steps.
The steps described in Figure 8-2 are essentially similar to those described in Section 6.3
for All-Volatile Treatment, except that reference should be made to the CT(2) guidelines,
instead of the AVT guidelines. Note that additional care is required to avoid excessive
8-4
carryover of boiler water impurities and conditioning chemicals, sodium hydroxide,

into the steam.
Under Step 6, excursions affecting (lowering) the pH must be corrected immediately by
feeding 1-2 ppm of sodium hydroxide to the boiler water. Match the sodium hydroxide
to the chloride concentration. Do not overfeed sodium hydroxide. Avoid excess
carryover of boiler water impurities into the steam.
Shutdown
The basic considerations outlined in Section 6.3 for AVT apply during shutdown for
Caustic Treatment, with the addition that special care has to be taken to prevent any
carryover of sodium hydroxide from the boiler water, as this could lead to stress
corrosion of austenitic components in the steam circuit.
A road map showing a scheme for shutdown of a drum boiler unit with an all-ferrous
amended in the light of operating experience. The road map, Figure 8-3, can be
divided into 5 steps.
(2)
for All-Volatile Treatment, except that reference should be made to the CT guidelines,
carryover of boiler water impurities and conditioning chemicals, sodium hydroxide,
into the steam.
Under Steps 4 and 5, excursions affecting (lowering) the pH must be corrected
immediately by feeding 1-2 ppm of sodium hydroxide to the boiler water. Match the
sodium hydroxide to the chloride concentration. Do not overfeed sodium hydroxide.
Avoid excess carryover of boiler water impurities into the steam.
treatment, except that additional care is required to avoid carryover of boiler water
impurities and conditioning chemical, sodium hydroxide, into the steam. Control of the
boiler water purity can be achieved by blowdown with drum boilers.
Cycling and Peaking

8-5

Step 1
No
Is system full?
Step 2
Yes
Step 4

low O2 scavenger?
(Section 4)
Step 3
Fill system per

CT guidelines
Yes
No

Refill per CT guidance
Step 5

water per CT
guidance?
Yes

and Fe to 100 ppb
Step 5
Proceed with
startup
Step 5
Fire to boiler
Step 6
Yes

Monitor chemical parameters,

especially sodium in steam
Step 6
Step 6

within CT guidelines by

Step 7
and load
Figure 8-2 CT - Startup of Drum Boilers with All-Ferrous Feedwater Heaters
8-6

Step 1
Normal cycling and
peaking operation
Step 2
Yes
No
Planned outage
Step 2
Yes
No
Yes
Step 3
Isolate and repair
leak, usually allow
continued operation
Yes
Condenser leak
fresh water cooling
No
Step 4
Yes
Condenser leak
sea water cooling
No
Step 5
utilized, otherwise
immediate shutdown
Consider chemical
Step 4
Orderly shutdown,
otherwise
immediate shutdown

Step 3
Step 2
Unplanned outage
Use short term

layup procedure
(Section 4)
Step 5
Yes
Chemical intrusion
Figure 8-3 CT - Shutdown of Drum Boilers with All-Ferrous and Mixed Metallurgy
Feedwater Heaters
Layup
The layup procedure is the same as described in Section 6.3 for All-Volatile Treatment.
8.3 MIXED METALLURGY FEEDWATER HEATING SYSTEMS

8-7
Copper in high pressure boilers can be carried over into the steam and deposited on
and the absence of reducing conditions in the feedwater is the main cause of copper
transport around the circuit.
It is worth reiterating(4) that startups are generally considered to be the periods of
(ORP < 0mV) is not maintained. Air in-leakage into the LP feedwater circuits increases
(4)
the growth of non-protective copper oxides and copper transport. The EPRI Guiding
Principles for successful operation of units with copper alloys are:
x



Many of the features discussed in Section 6 on All-Volatile Treatment also apply to

Caustic Treatment, with the proviso that particular care has to be taken in controlling
the concentration of sodium hydroxide in the boiler water and carry over into the
steam. This Section 8.3 of the guidlines will concentrate on the additional
considerations for Caustic Treatment and mixed Fe-Cu metallurgy feedwater heating
systems.
8-8
Current Guidelines
The current guidance on caustic treatment for drum boilers with mixed Fe-Cu
metallurgy feedwater systems are given in Figure 8-1 for reheat plants, including the
core parameters. The normal limits and three action levels for sodium, chloride,
sulfate, copper, silica and cation conductivity in boiler water are given in the EPRI (2)
report on Sodium Hydroxide Conditioning the Boiler Water of Drum-Type Boilers.
Non-reheat plant were not considered.
Startup
The basic considerations outlined in Section 6.4 for AVT with mixed Fe-Cu metallurgy
feedwater heating systems, also apply during startup for Caustic Treatment, with the
addition that special care has to be taken to prevent any carryover of sodium hydroxide
in the boiler water, as this could lead to stress corrosion of austenitic components in the
steam circuit. Care is required to minimise the ingress of oxygen to reduce the
corrosion of copper alloys.
The presence of oxygen also assists the transport of copper into the steam, increasing
the risk of deposition in the superheater and high pressure turbine. It is also important
to ensure that the pH, cation conductivity and chloride concentration are within the
(2)
limits given in the EPRI guidance document for boiler water. Hydrazine (or volatile
reducing agents) should not be eliminated from plants with mixed Fe-Cu feedwater
systems.
As mentioned previously, special care has to be taken to avoid excessively high
concentrations of sodium hydroxide in the boiler water and carryover of sodium
hydroxide into the steam. This can be prevented by carefully monitoring sodium in
steam. The steps used during startup will be plant specific and, depending on the
practicality, the following stages should be monitored, at least during a trial period:
Circuit Monitoring

the feedwater

copper
pH, NaOH or specific conductivity, cation

conductivity, chloride, and corrosion
products

steam

copper
8-9
At full load, the values given in the EPRI (2) guidance document should be achieved.
parameters are within the EPRI action levels 1-3, see Figure 8-1. The core parameters,
sodium, cation conductivity and oxygen given in the EPRI guidance document(2) should
be monitored at the condensate pump discharge, condensate polisher outlet (if
installed), economizer inlet, boiler water (preferably at downcomer), including pH and
specific conductivity or NaOH, and steam, including copper. The normal operating
levels, as given in the EPRI guidance document, should be achieved as soon as possible.
These are given in Figure 8-1.
operating experience. Section 3 explains how the action levels can be utilized during
unit startup. The cumulative operating hours per year for which the various action
loaded units.
startup, it may be necessary to adopt to another form of chemical conditioning, such as
phosphate. The Selection and Optimization document provides advice and guidance on
(3)
the optimum boiler water and feedwater choices for drum units . The procedure can
normally be curtailed for warm and hot starts. The road map, Figure 8-4, can be
divided into 7 steps.
carryover of boiler water impurities and the conditioning chemicals, sodium
hydroxide, into the steam. Compared to units with all-ferrous feedwater heating
systems, additional considerations are required for units with mixed Fe-Cu feedwater
heaters to reduce the risk of copper corrosion and transport, due to the ingress of
oxygen.
Under Step 6, excursions affecting (lowering) the pH must be corrected immediately by
feeding 1-2 ppm of sodium hydroxide to the boiler water. Match the sodium
hydroxide to the chloride concentration. Do not overfeed sodium hydroxide. Avoid
8-10

Step 2
No
Is system full?
Step 2
Yes
Step 4

low O2 scavenger?
(Section 4)
Step 3
Fill system per

CT guidelines
Yes
No

Refill per CT guidelines
Step 5

water per CT
guidelines?
Step 5
Yes
Proceed with
startup
Step 5
Fire to boiler
Step 6
Yes

Monitor chemical parameters,

especially sodium in steam
Step 6
Step 6

within CT guidelines by

Step 12
and load
Figure 8-4 CT - Startup of Drum Boilers with Mixed Fe-Cu Metallurgy Feedwater
Heaters
Shutdown
Information is given in Section 4 on the procedures generally applicable to shutdown,
and below for various planned shutdown conditions.
The basic considerations outlined in Section 6.4 for AVT with mixed Fe-Cu metallurgy
feedwater systems, also apply during shutdown for Caustic Treatment, with the
8-11
addition that special care has to be taken to prevent any carryover of sodium hydroxide
from the boiler water, as this could lead to stress corrosion of austenitic components in
the steam circuit. Care is required to minimise the ingress of oxygen to reduce the
corrosion of copper alloys.
A road map showing a scheme for shutdown of a drum boiler an with mixed Fe-Cu
amended in the light of operating experience. The road map, Figure 8-3, can be divided
into 5 steps.
The steps described in Figure 8-3 are essentially similar to those described in Section 6.
carryover of boiler water impurities and the conditioning chemicals, sodium
hydroxide, into the steam. Compared to units with all-ferrous feedwater heating
systems, additional considerations are required for units with mixed Fe-Cu feedwater
heaters to reduce the risk of copper corrosion and transport, due to the ingress of
oxygen.
Under Steps 4 and 5, excursions affecting (lowering) the pH must be corrected
immediately by feeding 1-2 ppm of sodium hydroxide to the boiler water. Match the
sodium hydroxide to the chloride concentration. Do not overfeed sodium hydroxide.
Avoid excess carryover of boiler water impurities into the steam.
Cycling and Peaking

Layup
The layup procedure is the same as described in Section 6.4 for All-Volatile Treatment.
8.4 REFERENCES
1. Cycle Chemistry Guidelines for Fossil Plants: All-Volatile Treatment. Electric Power
2. Sodium Hydroxide for Conditioning the Boiler Water of Drum-Type Boilers. Electric
Power Research Institute, Palo Alto, Calif. EPRI TR-105041. April 1996
8-12
4. State of Knowledge of Copper in Fossil Plant Cycles. Electric Power Research Institute,
8-13

EPRI Start Up, Lay Up & Shut Down Guidelines For Chemist

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Cycling, Startup, Shutdown, and

Layup Fossil Plant Cycle Chemistry

Final Report, August 1998

EPRI Project Manager

DISCLAIMER OF WARRANTIES AND LIMITATION OF LIABILITIES

EPRI Licensed Material

Phosphate treatment for drum boiler units,

All-Volatile treatment for drum and once-through units,

Oxygenated treatment for drum and once-through units,

Caustic treatment for drum units,

and three feedwater treatments:

Oxygenated treatment for all-ferrous metallurgy systems.

EPRI Licensed Material

Section 4 provides information on layup and shutdown considerations common to most

EPRI Licensed Material

EPRI Licensed Material

1 INTRODUCTION ................................................................................................................. 1-1

EPRI Licensed Material

2.5 EFFECTS OF STEAM CYCLE DESIGN AND OPERATION ..................................... 2-29

EPRI Licensed Material

3.8 OPERATING PROCEDURES.................................................................................... 3-10

EPRI Licensed Material

6.1 INTRODUCTION.......................................................................................................... 6-1

EPRI Licensed Material

Current Normal Operating Guidelines ........................................................................... 7-12

EPRI Licensed Material

EPRI Licensed Material

EPRI Licensed Material

EPRI Licensed Material

EPRI Licensed Material

1.1 OVERVIEW OF THE EPRI FOSSIL PLANT CYCLE CHEMISTRY

To eliminate boiler tube failures related to cycle chemistry

To develop optimized feedwater treatment:

elimination of serious flow-accelerated corrosion (FAC)

To eliminate the need for boiler chemical cleaning

To provide simple, reliable cycle chemistry instrumentation and control:

core levels of instrumentation for all plants

direct on-line, in-situ instruments

To shorten the startup period by:

EPRI Licensed Material

optimization of shutdown, lay-up and startup chemistry

the elimination of unnecessary chemical holds in the startup sequence

To provide the optimum managerial approach in support of cycle chemistry

Deposition around the cycle

Steam chemistry and corrosion in the phase transition zone (PTZ)

Volatility of Salts in Steam Cycles

EPRI Licensed Material

EPRI Licensed Material

EPRI Licensed Material

very difficult. Also, an increasing number of utilities experienced serious internal

Departure from nucleate boiling (DNB) 12 hours in duration

Phosphate concentration to 10 ppm

Sodium to phosphate molar ratios ranging from 1.84.0

Magnetite deposition of 4 mg/cm2 (~4 grams/ft2)

Low chloride and silica contamination

EPRI Licensed Material

Deposition and Chemical Cleaning

Steam, Chemistry and Corrosion in the Phase Transition Zone (PTZ)

EPRI Licensed Material

1.2 EPRI FOSSIL PLANT GUIDELINES AND MANAGEMENT APPROACHES

Phosphate treatment guidelines to cover phosphate treatment (PT) and equilibrium

Oxygenated treatment for once-through and drum units(14)

All-volatile treatment for once-through and drum units(15)