Interim Cycle Chemistry Guidelines For Combined Cycle Heat Recovery Steam Generators (HRSGS) - TR-110051

Interim Cycle Chemistry Guidelines
for Combined Cycle Heat Recovery

Steam Generators (HRSGs)
TR-110051
Final Report, November 1998
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EPRI Project Manager

R. B. Dooley
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CITATIONS
This report was prepared by
Electric Power Research Institute, Inc.
3412 Hillview Avenue
Palo Alto, California 94304
Authors
R. B. Dooley
A. Aschoff
M. Ball
A. Bursik
F. Pocock
K. J. Shields
This report describes research sponsored by EPRI.
The report is a corporate document that should be cited in the literature in the
following manner:
Interim Cycle Chemistry Guidelines for Combined Cycle Heat Recovery Steam Generators
(HRSGs), EPRI, Palo Alto, CA: 1998. TR-110051.
iii
REPORT SUMMARY
Combined cycle/heat recovery steam generator (HRSG) plants are relatively new
sources of generation with efficiencies approaching 60%. The purity of the water and
steam is central to ensuring these efficiency levels, as well as the overall plant
availability and reliability. These guidelines will assist operators in developing an
effective overall cycle chemistry program.
Background
HRSGs were originally designed to produce steam at one pressure level. Todays HRSG
is complex and may have three pressure levels with superheat and reheat and may be
once-through or recirculating. In the near future, combined cycles will consist of a oncethrough HRSG and one or two drum HRSGs. The existence of so many system designs
has made it difficult to specify cycle chemistry guidelines that can cover each unique
configuration. Consequently, an increasing number of HRSG failures have occurred
that are influenced by the cycle chemistry. The guidelines in this document build on the
extensive body of EPRI research for conventional fossil plants to specifically address
the needs and characteristics of combined cycle/HRSGs and to avoid operating
problems and failure.
Objectives
To consolidate a comprehensive approach to the selection and optimization of cycle
chemistry for combined cycle/HRSG plants.
Approach
EPRI developed an initial skeleton of the guidelines for discussion with the EPRI HRSG
Cycle Chemistry Group (HCCG). This group provided comments and suggestions.
Following these initial activities, EPRI and five of its cycle chemistry consultants
developed two draft documents that were circulated to the 20 members of the HCCG
for review and comment.
Results
The guidelines contain detailed procedures and road maps for selecting and optimizing
the feedwater and boiler water treatments for combined cycle units containing drum
and once-through HRSGs. There are five different chemistry regimes that are available
for drum-type HRSGs and two for once-through units. Feedwater systems for HRSGs
are relatively simple, but the choice of one of three chemistries is crucial to the reliable
operation of the combined cycle. Included for each chemistry is a set of target values
and action levels for critical sample points throughout the water and steam cycle. A
separate section has been developed for shutdown and layup considerations for
HRSGs.
EPRI Perspective
Following these guidelines, an operator will be able to select, optimize, and maintain a
cycle chemistry control program for combined cycle units that avoids operating
problems and HRSG failures.
These guidelines are considered interim. The target values and action levels will be
reviewed over the next few years in the light of continuing research, together with onsite monitoring at several combined cycle plants as operators implement these
guidelines.
Combined cycle plants are minimally staffed from the chemistry viewpoint,
emphasizing the need for simple, reliable instrumentation alarmed for immediate
action. EPRI will be expanding its Cycle Chemistry Advisor for conventional fossil
plants to encompass combined cycle plants.
TR-110051
Interest Categories
Combustion turbine/combined cycle plants
Advanced combustion turbine & cycles
Fossil steam plant o&m cost reduction
Applied science & technology
Keywords
Combined cycle power plants
Heat recovery steam generator (HRSGs)
Cycle chemistry
Steam
vi
EPRI Licensed Material
ABSTRACT
Combined cycle/HRSG plants are a relatively new source of more efficient generation.
Over the last 5-8 years the designs have become remarkably complex with the HRSG
either consisting of up to three pressure drum systems, once-through systems, or
combined drum/once-through systems. Many different variations are also available
within these basic designs.
This increasing level of complexity has been accompanied by numerous failures and
operating problems. The selection and optimization of HRSG feedwater and boiler
water to avoid operating problems and failure are the primary focus of this new
guideline.
Five different chemistry regimes are available for drum type HRSGs (PT, EPT, AVT,
CT, and OT), while two chemistries (AVT and OT) are available for once-through units.
The feedwater system for HRSGs is much simpler than in conventional fossil plants,
but the same three different chemistries are available (AVT, AVT without a reducing
agent, and OT).
The user of this guidelines is first referenced to Section 9 where advice and guidance is
provided on selecting the feedwater and boiler water for each individual HRSG circuit,
and on optimizing the chosen treatment. Operating guidelines, target values and
action levels for each of the chemistries are provided in Sections 3-8, which include
information on startup and shutdown. Separate guidance is provided on layup in
Section 10.
The cycle chemistry control philosophy for the combined cycle/HRSG systems has
been based on conductivity measuring instrumentation. Emphasis has also been placed
on a comprehensive level of monitoring parameters for commissioning and
troubleshooting.
These guidelines are considered interim. The target values and action levels will be
reviewed over the next few years in the light of subsequent research and operating
experience implementing these guidelines.
vii
ACKNOWLEDGMENTS
The authors of these guidelines
R. B. Dooley, EPRI
A. Aschoff, EPRI Consultant
M. Ball, EPRI Consultant
A. Bursik, EPRI Consultant
F. Pocock, EPRI Consultant
K. J. Shields, EPRI Consultant of Sheppard T. Powell Associates, LLC
acknowledge the contributions from the following members of the HRSG Cycle
Chemistry Group:
J. Bellows
G. Bignold
J. Daiber
D. Foussat
F. Gabrielli
R. Harries
M. Macrae
K. McGrath
S. Medeiros
J. Schroeder
A. Selby
F. Shoemaker
W. Stroman
R. Svoboda
W. Urion
A. Whitehead
D. Wiltsey
R. Wulff
R. Woulfe
Westinghouse, USA
National Power, UK
Vogt-Nem, USA
Alstom Energy Systems
ABB Combustion, USA
PowerGen, UK
Mitsui Babcock, UK
Consultant, UK
New England Power, USA
Nooter/Eriksen, USA
Puckorius & Associates, USA
Westinghouse, USA
San Diego Gas and Electric, USA
ABB Power Generation, Switzerland
Conectiv, USA
GE, USA
NALCO, USA
Siemens, Germany
Contact Energy, New Zealand
The authors also want to thank S. Paterson of Aptech Engineering Services and X. Du of
China Light and Power for assisting with the metallography of failed HRSG tubing.
ix
All the graphics in the guideline were produced by Marilyn Winans of EPRIs Graphic
Design Office. The word processing and organization were completed by Lorrain
Sargent of Pacific Publications in San Francisco.
CONTENTS
1 INTRODUCTION ................................................................................................................. 1-1

1.1 BRIEF HISTORY .......................................................................................................... 1-1
1.2 TYPES OF CYCLES AND STEAM GENERATORS ..................................................... 1-2
1.3 MATERIALS ............................................................................................................... 1-11
1.4 HEATING SURFACE .................................................................................................. 1-11
1.5 WATER QUALITY AND QUANTITY CONSIDERATIONS .......................................... 1-11
Multiple Pressure Drum HRSGs.................................................................................... 1-13
Cogeneration ................................................................................................................ 1-14
Nitrogen Oxide (NOx) Control in Gas Turbines .............................................................. 1-14
Attemperation for Steam Turbines ................................................................................ 1-15
Reducing Agent (Oxygen Scavenger) Usage ............................................................... 1-16
1.6 COMBINED CYCLE/HRSG CHEMISTRY TREATMENTS......................................... 1-16
Phosphate Treatment Applicability................................................................................ 1-16
All-Volatile Treatment (AVT) Applicability ...................................................................... 1-17
Caustic Treatment Applicability ..................................................................................... 1-17
Oxygenated Treatment (OT) Applicability ..................................................................... 1-17
1.7 BALANCE OF PLANT................................................................................................. 1-18
Deaeration .................................................................................................................... 1-18
Feedwater Heating........................................................................................................ 1-19
Makeup Requirements .................................................................................................. 1-19
Condensate Polishing ................................................................................................... 1-20
Condenser .................................................................................................................... 1-21
1.8 CHEMICAL CLEANING .............................................................................................. 1-21
1.9 CHEMISTRY PROBLEMS IN HRSG UNITS.............................................................. 1-22
Carryover and Turbine Damage.................................................................................... 1-25
Corrosion During HRSG Unit Shutdown and Idle Periods............................................. 1-25
xi
1.10 HRSG TUBE FAILURES.......................................................................................... 1-26

Flow-Accelerated Corrosion (FAC) in HRSG Evaporator Tubing ...................................... 1-26
Under-Deposit Corrosion in HRSG Evaporator Tubing ..................................................... 1-27
Corrosion Fatigue ............................................................................................................. 1-27
1.11 HRSG CYCLE CHEMISTRY DIAGRAMS................................................................ 1-31
1.12 REFERENCES AND SOURCES .............................................................................. 1-35
2 RATIONALE FOR HRSG CHEMICAL TREATMENTS, SAMPLE POINTS, ACTION
LEVELS AND TARGET VALUES .......................................................................................... 2-1
2.1 INTRODUCTION.......................................................................................................... 2-1
Phosphate (PT) and Equilibrium Phosphate (EPT) HRSG Boiler Water Control............. 2-2
Drum Units on All-Volatile Treatment .............................................................................. 2-5
Cycles with Once-Through Units on All-Volatile Treatment (AVT)................................... 2-6
Caustic Treatment (CT) of HRSG Drum Boilers .............................................................. 2-7
Oxygenated TreatmentOnce-Through and Drum Units ............................................... 2-7
2.2 GUIDELINE DERIVATION PHILOSOPHY.................................................................... 2-9
2.3 RATIONALE FOR SAMPLE POINTS ......................................................................... 2-15
Reheat Steam and Superheated Steam ....................................................................... 2-18
Saturated Steam (Drum HRSGs Only).......................................................................... 2-18
HRSG Boiler Water ....................................................................................................... 2-18
Economizer Inlet(s) and Attemperation Water............................................................... 2-19
Deaerator Inlet (If Applicable)........................................................................................ 2-19
Deaerator Outlet (If Applicable)..................................................................................... 2-19
Condensate Polisher Effluent (if Applicable) ................................................................. 2-19
Condensate Pump Discharge ....................................................................................... 2-20
Condenser Leak Detection Trays and/or Hotwell Zones (If Applicable) ........................ 2-20
Makeup Treatment System Effluent .............................................................................. 2-20
Condensate Storage Tank Effluent ............................................................................... 2-20
Air Removal System Exhaust........................................................................................ 2-20
2.4 TROUBLESHOOTING, COMMISSIONING AND CORE PARAMETERS ................... 2-21
2.5 RATIONALE FOR ACTION LEVELS .......................................................................... 2-23
2.6 RATIONALE FOR TARGET VALUES......................................................................... 2-24
Steam............................................................................................................................ 2-25
HRSG Boiler Water (Drum Units) .................................................................................. 2-25
xii
2.7 RATIONALE FOR TARGET VALUES OF INDIVIDUAL PARAMETERS .................... 2-29

Cation Conductivity ........................................................................................................... 2-30
Specific Conductivity......................................................................................................... 2-31
pH ..................................................................................................................................... 2-32
Dissolved Oxygen (Non OT units only) ............................................................................. 2-33
Dissolved Oxygen (OT Units)............................................................................................ 2-33
Sodium.............................................................................................................................. 2-34
Phosphate (Drum HRSGs on PT and EPT) ...................................................................... 2-35
Silica ................................................................................................................................. 2-38
Chloride ............................................................................................................................ 2-39
Sulfate .............................................................................................................................. 2-40
Sodium Hydroxide (Drum HRSGs on CT only) ................................................................. 2-42
Ammonia........................................................................................................................... 2-42
Reducing Agents such as Hydrazine (non OT units only)................................................. 2-42
Iron (and Copper, if Copper Alloys are Present) ............................................................... 2-43
Oxidizing-Reducing Potential (ORP)................................................................................. 2-44
Total Organic Carbon (TOC)............................................................................................. 2-44
Air In-Leakage .................................................................................................................. 2-44
2.8 GUIDELINE CUSTOMIZATION AND OPTIMIZATION ............................................... 2-46
2.9 REFERENCES ........................................................................................................... 2-46
3 CYCLES WITH DRUM HRSGs ON PHOSPHATE AND EQUILIBRIUM PHOSPHATE
TREATMENT (PT AND EPT) ................................................................................................. 3-1
3.1 INTRODUCTION TO EPT AND PT............................................................................... 3-1
3.2 GUIDELINES FOR PHOSPHATE TREATMENTS........................................................ 3-2
3.3 TARGET VALUES FOR HRSGs WITH REHEAT ON PT ............................................. 3-2
3.4 TARGET VALUES FOR PLANTS WITHOUT REHEAT ON PT .................................. 3-18
3.5 NORMAL OPERATION FOR PT................................................................................. 3-19
Phosphate Hideout and Its Control ............................................................................... 3-19
Reaction to Contaminants in Boiler Cycle ..................................................................... 3-20
Startup and Shutdown Operation.................................................................................. 3-21
Hot Startup and the Impact of Hideout.......................................................................... 3-23
3.6 OVERVIEW OF EQUILIBRIUM PHOSPHATE TREATMENT (EPT)........................... 3-23
3.7 GUIDELINES FOR EPT.............................................................................................. 3-24
xiii
Target Values for HRSGs With Reheat on EPT ............................................................ 3-25

Target Values for HRSGs Without Reheat on EPT ....................................................... 3-26
3.8 CONSIDERATIONS IN CONVERTING TO EQUILIBRIUM PHOSPHATE
TREATMENT (EPT).......................................................................................................... 3-35
3.9 CONVERTING A BOILER TO EQUILIBRIUM PHOSPHATE TREATMENT ............... 3-35
3.10 OPERATION DURING UPSET CONDITIONS WITH EPT........................................ 3-38
3.11 UNIT STARTUP AND SHUTDOWN.......................................................................... 3-39
Cold Startup .................................................................................................................. 3-39
Unit Trip With Normal Contaminant Concentrations...................................................... 3-39
Unit Shutdown............................................................................................................... 3-39
3.12 REFERENCES ......................................................................................................... 3-40
4 CYCLES WITH DRUM HRSGs ON ALL-VOLATILE TREATMENT (AVT) ......................... 4-1
4.1 INTRODUCTION TO ALL-VOLATILE TREATMENT ................................................... 4-1
4.2 USE OF REDUCING AGENTS (OXYGEN SCAVENGERS)........................................ 4-2
4.3 GUIDELINES FOR AVT............................................................................................... 4-2
4.4 AVT GUIDANCE .......................................................................................................... 4-2
4.5 TARGET VALUES FOR PLANTS WITH REHEAT ON AVT ........................................ 4-3
4.6 TARGET VALUES FOR PLANTS WITHOUT REHEAT ............................................. 4-12
4.7 CONVERTING A HRSG DRUM BOILER CYCLE TO AVT OR OPTIMIZING THE
CURRENT AVT ................................................................................................................ 4-13
4.8 NORMAL OPERATION FOR HRSG DRUM UNITS ON AVT .................................... 4-19
4.9 REACTION TO CONTAMINANTS IN THE CYCLE.................................................... 4-20
4.10 STARTUP AND SHUTDOWN OPERATION ............................................................ 4-21
4.11 CYCLING AND PEAKING OPERATION.................................................................. 4-22
4.12 REFERENCES AND BIBLIOGRAPHY .................................................................... 4-23
5 CYCLES WITH ONCE-THROUGH HRSGs ON ALL-VOLATILE TREATMENT (AVT)....... 5-1
5.1 INTRODUCTION.......................................................................................................... 5-1
5.2 AVT GUIDANCE .......................................................................................................... 5-6
Target Values ..................................................................................................................... 5-6
5.3 NORMAL OPERATION FOR ONCE-THROUGH HRSG UNITS ON AVT.................... 5-8
5.4 REACTION TO CONTAMINANTS IN THE CYCLE...................................................... 5-8
5.5 STARTUP AND SHUTDOWN OPERATION ................................................................ 5-9
Cold Start ........................................................................................................................ 5-9
xiv
Hot Start.......................................................................................................................... 5-9

5.6 REFERENCES ............................................................................................................ 5-9
6 CYCLES WITH DRUM HRSGs ON CAUSTIC TREATMENT (CT)...................................... 6-1
6.1 INTRODUCTION TO CAUSTIC TREATMENT ............................................................ 6-1
6.2 GUIDELINES FOR CAUSTIC TREATMENT ............................................................... 6-2
6.3 TARGET VALUES FOR PLANTS ON CAUSTIC TREATMENT .................................. 6-4
6.4 NORMAL OPERATION FOR CAUSTIC TREATMENT ................................................ 6-7
6.5 REACTION TO CONTAMINANTS IN THE CYCLE.................................................... 6-17
6.6 STARTUP AND SHUTDOWN OPERATION .............................................................. 6-19
6.7 APPROACH TO DEVELOPING OPTIMUM CAUSTIC TREATMENT........................ 6-19
6.8 REFERENCES .......................................................................................................... 6-23
7 CYCLES WITH DRUM HRSGs ON OXYGENATED TREATMENT (OT) ............................ 7-1
7.1 INTRODUCTION TO OXYGENATED TREATMENT FOR DRUM UNITS.................... 7-1
7.2 OXYGENATED TREATMENT GUIDANCE.................................................................. 7-2
7.3 CONVERTING A DRUM HRSG TO OT AND/OR OPTIMIZING THE CYCLE
CHEMISTRY....................................................................................................................... 7-6
7.4 NORMAL OPERATION FOR DRUM HRSG UNITS ON OT ........................................ 7-9
Chemical Dosing ............................................................................................................. 7-9
Establishing the Oxygen Recirculation Ratio................................................................. 7-10
7.5 REACTION TO CONTAMINANTS IN THE HRSG BOILER CYCLE .......................... 7-10
Startup .......................................................................................................................... 7-11
Shutdown ...................................................................................................................... 7-12
Layup ............................................................................................................................ 7-13
7.7 CYCLING AND PEAKING OPERATION.................................................................... 7-13
7.8 REFERENCES .......................................................................................................... 7-14
8 CYCLES WITH ONCE-THROUGH UNITS ON OXYGENATED TREATMENT ................... 8-1
8.1 INTRODUCTION TO OXYGENATED TREATMENT FOR ONCE-THROUGH
UNITS ................................................................................................................................. 8-1
8.2 OXYGENATED TREATMENT GUIDANCE.................................................................. 8-5
8.3 CONVERTING A ONCE-THROUGH HRSG TO OT AND/OR OPTIMIZING THE
CYCLE CHEMISTRY .......................................................................................................... 8-5
8.4 NORMAL OPERATION FOR ONCE-THROUGH UNITS ON OT ................................. 8-9
xv
Chemical Dosing ............................................................................................................. 8-9

8.5 REACTION TO CONTAMINANTS IN THE CYCLE...................................................... 8-9
Startup .......................................................................................................................... 8-10
Shutdown ...................................................................................................................... 8-10
Layup ............................................................................................................................ 8-11
8.7 CYCLING AND PEAKING OPERATION.................................................................... 8-12
8.8 REFERENCES .......................................................................................................... 8-12
9 APPROACH TO DEVELOPING OPTIMUM CHEMICAL TREATMENT FOR HRSGs
ASSOCIATED WITH COMBUSTION TURBINE/COMBINED CYCLES................................. 9-1
9.1 INTRODUCTION.......................................................................................................... 9-1
9.2 OVERVIEW OF THE SELECTION AND OPTIMIZATION PROCESS ......................... 9-2
9.3 SELECTION OPTIONS FOR FEEDWATER TREATMENT FOR HRSG CYCLES ...... 9-3
Objectives for Feedwater Treatment................................................................................... 9-3
Typical Feedwater Problems............................................................................................... 9-3
Selection of Feedwater Treatment...................................................................................... 9-4
Water Chemistry ................................................................................................................. 9-5
9.4 OPTIMIZATION OF FEEDWATER CHEMISTRY FOR HRSG/COMBINED
CYCLE UNITS .................................................................................................................... 9-8
9.5 SELECTION OF OPTIMUM HRSG DRUM BOILER WATER TREATMENT.............. 9-12
Boiler Water Selection for Individual Drum Pressure Cycles............................................. 9-15
Considerations for Multiple Pressure Drum Cycles ........................................................... 9-23
9.6 REFERENCES .......................................................................................................... 9-24
10 SHUTDOWN AND LAYUP CONSIDERATIONS FOR COMBINED CYCLE/HRSG
SYSTEMS............................................................................................................................. 10-1
10.1 INTRODUCTION...................................................................................................... 10-1
10.2 LAYUP PRACTICES................................................................................................ 10-2
Short-term vs. Longterm Layup..................................................................................... 10-5
10.3 WET LAYUP ............................................................................................................ 10-6
10.4 DRY LAYUP USING DEHUMIDIFIED AIR............................................................... 10-7
10.5 PREHEATERS, FEEDWATER HEATERS, CONDENSER, REHEATER AND
STEAM TURBINES ........................................................................................................ 10-11
Steam Turbine............................................................................................................. 10-12
xvi
Preheater/Feedwater Side of Condensers and Preheater/Feedwater Heaters (if

utilized)........................................................................................................................ 10-13
Superheater ................................................................................................................ 10-13
Deaerator and Storage Tank....................................................................................... 10-13
10.6 LAYUP MONITORING ........................................................................................... 10-14
10.7 ENVIRONMENTAL CONSIDERATIONS ............................................................... 10-14
10.8 REFERENCES ...................................................................................................... 10-14
A MANUFACTURER'S HRSG CHEMISTRY GUIDELINES ...................................................A-1
Siemens Recommendations for the Chemical Treatment of the Steam Water Cycle of
HRSGs................................................................................................................................ A-1
xvii
LIST OF FIGURES
Figure 1-1 Simplified combined cycle system schematics.(1) ................................................... 1-3
Figure 1-2 Natural Circulation, vertical tubed, single pressure HRSG(2) .................................. 1-4
Figure 1-3 Forced Circulation, horizontal tubed, single pressure HRSG(2) .............................. 1-4
Figure 1-4 Natural circulation, horizontal tubed, multi-pressure HRSG(2) ................................ 1-5
Figure 1-5 Horizontal and vertical tube typical configurations for drum-type HRSGs(20) .......... 1-6
Figure 1-6 Temperature profile in single pressure HRSG(1)..................................................... 1-8
Figure 1-7 Once-through combustion turbine combined cycle(11,12) .......................................... 1-9
Figure 1-8 Combination drum and once-through HRSG(13) .................................................... 1-10
Figure 1-9 Approximate surface required in convection tube bank and vestibule for
various entering and leaving waste gas temperatures. ................................................. 1-12
Figure 1-10 Permissible Specific Deposit Weight Limits As A Function of Boiler
Pressure for Conventional Fossil Plants(17) .................................................................... 1-24
Figure 1-11 Flow-accelerated corrosion at the bend of a low pressure HRSG evaporator
tube. .............................................................................................................................. 1-28
Figure 1-12 Detail of the FAC shown in Figure 1-11. Note the typical chevron markings
in the FAC region and also the area of "excessive deposition" (box-like magnetite)
about 2 in. (5 cm) from the FAC. ................................................................................... 1-29
Figure 1-13 Acid phosphate corrosion in an HRSG high pressure evaporator tube (1500
psi, 10.3 MPa). HRSG was operated on congruent phosphate treatment with
additions of low molar ratio (2) Na:PO4 chemicals........................................................ 1-30
Figure 1-14 Incipient corrosion fatigue cracks in HRSG economizer tubing after only
about 4000 hours. ......................................................................................................... 1-30
Figure 1-15 Options for HRSGs/OTSGs ............................................................................... 1-32
Figure 1-16 Combustion Turbine/Combined Cycle Unit Three Pressure Drum HRSG
with Reheat. It should be noted that this diagram does not represent exactly any
operating unit. It is only illustrative for use in the chemistry cycle diagrams for
drum units in this guideline............................................................................................ 1-33
Figure 1-17 Combustion turbine/combined cycle unit with once-through HRSG and
reheat. It should be noted that this diagram does not represent exactly any
once-through units in this guideline............................................................................... 1-34
Figure 2-1 Historical Development of pH-Phosphate Control Ranges(3) .................................. 2-4
xix
Figure 2-2 Schematic of Operating Ranges of Boiler Water on Equilibrium Phosphate

Treatment (EPT), Congruent Phosphate Treatment (CPT) and Phosphate
Treatment (PT)................................................................................................................ 2-5
Figure 2-3 Comparison of AVT (upper) vs. OT (lower) indicating major difference in the
level of feedwater corrosion products exiting from the feedwater system in
conventional fossil plants. ............................................................................................... 2-8
Figure 2-4 Mollier Diagram for a Fossil Cycle. Illustrates Where Impurities Will
Concentrate and Promote Corrosion............................................................................. 2-11
Figure 2-5 Drum Boiler Mechanical Carryover. Monitoring should be conducted on
each HRSG drum to determine the mechanical carryover. ........................................... 2-13
Figure 2-6 Distribution Ratios for Common Boiler Water Contaminants ............................... 2-14
Figure 2-7 Influence of Air In-Leakage and Installed Air Removal Capacity on
Achievable Dissolved Oxygen Levels in the Condensate (1SCfm = 1.7sm3/h............... 2-45
Figure 3-1 Cycle Chemistry Diagram for an HRSG Drum Unit on Phosphate Treatment
(Plants With Reheat). It should be noted that this diagram does not represent
exactly any operating unit. It is only illustrative for use in the chemistry cycle
diagrams for drum type HRSG units. Operators should apply the
parameters/target boxes to their actual unit. These may need customization
according to Sections 1.11 and 9.5................................................................................. 3-7
Figure 3-2 Phosphate Treatment: Boiler Water Sodium and Phosphate vs. Operating
Pressure (HRSG/Combined Cycle Plants With Reheat).................................................. 3-9
Figure 3-3 Phosphate Treatment: Boiler Water Chloride vs. Operating Pressure
(HRSG/Combined Cycle Plants With Reheat)............................................................... 3-10
Figure 3-4 Phosphate Treatment: Boiler Water Sulfate vs. Operating Pressure
Figure 3-5 Phosphate Treatment: Boiler Water Silica vs. Operating Pressure
Figure 3-6 Phosphate Treatment: HRSG Boiler Water pH vs. Phosphate at Various
Ammonia Levels............................................................................................................ 3-13
Figure 3-7 Phosphate Treatment: Ammonia Concentration vs. pH for Various Carbon
Dioxide Concentrations ................................................................................................. 3-14
Figure 3-8 Phosphate vs. Specific Conductivity at Various Na to PO4 Molar Ratios (Vmol)
and as Phosphoric Acid(2) (The H3PO4 curve represents all sodium phosphate
ratios after cation exchange.)........................................................................................ 3-15
Figure 3-9 Phosphate Treatment (PT) HRSG Drum Water Specific Conductivity vs.
Operating Pressure. Molar Ratio Na:PO4 = 3.0 (Plants With Reheat) .......................... 3-16
Figure 3-10 Phosphate Treatment (PT) HRSG Drum Water Cation Conductivity vs.
Operating Pressure. Molar Ratio Na:PO4 = 3.0 (Plants With Reheat) .......................... 3-17
Figure 3-11 Schematic of Operating Ranges of Boiler Water on Equilibrium Phosphate
Treatment (PT).............................................................................................................. 3-21
Figure 3-12 Cycle chemistry diagram for an HRSG drum unit on equilibrium phosphate
treatment (plants with reheat). It should be noted that this diagram does not
represent exactly any operating unit. It is only illustrative for use in the chemistry
xx
cycle diagrams for drum type HRSG units. Operators should apply the
according to Sections 1.11 and 9.5............................................................................... 3-27
Figure 3-13 Equilibrium phosphate treatment: Boiler water sodium vs. operating
pressure (HRSG/combined cycle plants with reheat) .................................................... 3-29
Figure 3-14 Equilibrium phosphate treatment: Boiler water chloride vs. operating
Figure 3-15 Equilibrium phosphate treatment: Boiler water sulfate vs. operating
Figure 3-16 Equilibrium phosphate treatment: Boiler water silica vs. operating pressure
(HRSG/combined cycle plants with reheat)................................................................... 3-32
Figure 3-17 Equilibrium phosphate treatment (EPT): HRSG drum water specific
conductivity vs. operating pressure, molar ratio Na:PO4 = 3.0 (plants with reheat) ....... 3-33
Figure 3-18 Equilibrium phosphate treatment (EPT): HRSG drum water cation
conductivity vs. operating pressure, molar ratio Na:PO4 = 3.0 (plants with reheat) ....... 3-34
Figure 3-19 Road map for converting an HRSG boiler to equilibrium phosphate ................. 3-36
Figure 4-1 Cycle Chemistry Diagram for a HRSG Drum Unit on All-Volatile Treatment
Figure 4-2 All-Volatile Treatment: HRSG Drum Boiler Water Sodium vs. Operating
Figure 4-3 All-Volatile Treatment: HRSG Drum Boiler Water Chloride vs. Operating
Figure 4-4 All-Volatile Treatment: HRSG Drum Boiler Water Sulfate vs. Operating
Figure 4-5 All-Volatile Treatment: HRSG Drum Boiler Water Silica vs. Operating
Pressure (HRSG/Combined Cycle Plants With Reheat)................................................ 4-10
Figure 4-6 All-Volatile Treatment: HRSG Drum Boiler Water Cation Conductivity vs.
Operating Pressure (HRSG/Combined Cycle Plants With Reheat)............................... 4-11
Figure 4-7 Road Map to Convert a HRSG Drum Boiler Cycle with All-Ferrous Feedwater
to AVT and/or Develop the Optimum AVT. ................................................................... 4-15
Figure 5-1 Cycle Chemistry Diagram for a Once-Through HRSG Unit on All-Volatile
Treatment. It should be noted that this diagram does not represent exactly any
once-through HRSG units. Operators should apply the parameter/target boxes to
their actual unit................................................................................................................ 5-3
Figure 5-2 Theoretical Relationship Between Specific Conductivity and pH for Ammonia
Solutions. ........................................................................................................................ 5-5
Figure 5-3 Ammonia Concentration vs. pH for Various Carbon Dioxide Concentrations ........ 5-7
xxi
Figure 6-1 Cycle Chemistry Diagram for an HRSG Drum Unit on Caustic Treatment
(Plants with Reheat). It should be noted that this diagram does not represent
Figure 6-2 Caustic Treatment: HRSG Boiler Water pH vs. Operating Pressure
(HRSG/Combined Cycle Plants) ..................................................................................... 6-8
Figure 6-3 Caustic Treatment: Boiler Water Cation Conductivity vs. Operating Pressure
(HRSG/Combined Cycle Plants) ..................................................................................... 6-9
Figure 6-4 Caustic Treatment: Boiler Water Specific Conductivity vs. Operating
Pressure (HRSG/Combined Cycle Plants) .................................................................... 6-10
Figure 6-5 Caustic Treatment: Boiler Water Sodium Hydroxide vs. Operating Pressure
(HRSG/Combined Cycle Plants) ................................................................................... 6-11
Figure 6-6 Caustic Treatment: HRSG Boiler Water Chloride vs. Operating Pressure
Figure 6-7 Caustic Treatment: Boiler Water Sulfate vs. Operating Pressure
Figure 6-8 Caustic Treatment: Boiler Water Sodium vs. Operating Pressure
Figure 6-9 Caustic Treatment: Boiler Water Silica vs. Operating Pressure
Figure 6-10 Relationship between Specific Conductivity, Cation Conductivity and pH at
25C for HRSG Boiler Water with Caustic Treatment.................................................... 6-16
Figure 6-11 Relationship between pH and Equivalent Sodium Hydroxide Concentration
at 25C .......................................................................................................................... 6-18
Figure 6-12 Road Map for Conversion of HRSG/Combined Cycle Plants to Caustic
Treatment...................................................................................................................... 6-20
Figure 6-13 Road Map to Optimize HRSG/Combined Cycle Plants on Caustic
Treatment...................................................................................................................... 6-21
Figure 7-1 Cycle Chemistry Diagram for an HRSG Drum Unit on Oxygenated Treatment
parameters/target boxes to their actual unit. These may need custimization
according to sections 1-11 and 9-5. ................................................................................ 7-3
Figure 7-2 Oxygenated treatment: HRSG drum boiler water cation conductivity vs.
operating pressure (HRSG/combined cycle plants with reheat) ...................................... 7-5
Figure 7-3 Roadmap - Converting a drum HRSG to OT and/or optimizing the cycle
chemistry......................................................................................................................... 7-7
Figure 8-1 Cycle Chemistry Diagram for a Once-Through HRSG Unit Operating on
Oxygenated Treatment. It should be noted that this diagram does not represent
xxii
diagrams for once-through HRSG units. Operators should apply the

parameters/target boxes to their actual unit. ................................................................... 8-3
Figure 8-2 Road MapConverting a Once-Through HRSG to OT and/or Optimizing the
Cycle Chemistry .............................................................................................................. 8-6
Figure 9-1 Changes in Oxidizing Reducing Potential (ORP) and Feedwater Iron Levels
(Fe) at the Economizer Inlet when Hydrazine (N2H4) is Gradually Reduced on a
600 MW Drum Unit with an All-Ferrous Feedwater System. ........................................... 9-6
Figure 9-2 Schematic Representation of Oxide Formed on Iron-Based Feedwater
Surfaces During Operation with Deoxygenated AVT. ..................................................... 9-7
Figure 9-3 Schematic Representation of Oxide Formed on Iron-Based Feedwater
Surfaces During Operation with OT. ............................................................................... 9-7
Figure 9-4 Road Map for Optimizing Feedwater Treatment for All-Ferrous OnceThrough and Drum Units ................................................................................................. 9-9
Figure 9-5 Road Map for Drum HRSG Boiler Water Treatment Selection ............................ 9-14
Figure 10-1 Corrosion rate of steel relative to humidity of air................................................ 10-8
Figure 10-2 Rotary desiccant dehumidifier(17) ........................................................................ 10-9
Figure 10-3 Steamside Dehumidification Flow.................................................................... 10-10
Figure 10-4 Turbine: Dry Layup Using Dehumidified Air(23).................................................. 10-12
Figure 10-5 Dry Layup of 107 MW Turbine Showing Measured Values of Temperature
and Air Humidity.......................................................................................................... 10-13
xxiii
LIST OF TABLES
Table 1-1 Sample Cycle Efficiencies and Heat Rates............................................................. 1-1
Table 2-1 HRSG Cycle Chemistry Monitoring Parameters ................................................... 2-17
Table 3-1 Differences Between Normal Action Levels for Reheat and Non-Reheat
HRSG Units on PT ........................................................................................................ 3-18
Table 3-2 Differences Between Normal Action Levels for Reheat and Non-Reheat Units
on EPT .......................................................................................................................... 3-26
Table 4-1 Differences Between Normal Action Levels for Reheat and Non-Reheat Units
on AVT .......................................................................................................................... 4-12
Table 10-1 Shutdown and Layup Alternatives Showing Advantages and Disadvantages
for Each Alternative....................................................................................................... 10-3
xxv
1
INTRODUCTION
1.1 BRIEF HISTORY

The idea of using waste energy for increased steam generation in industry has been
around for many years. The progressive increase in fuel costs, the need to capture heat
from various industrial processes and increasingly stringent environmental regulations
(1)
have created the need for using waste heat to its fullest potential . During the last ten
years, substantial progress has been made in the development and commercialization
of technology for efficient generation of steam from waste energy.
In the power industry, the waste heat from one power system such as a gas turbine can
serve as a heat source for a steam turbine cycle. Such combined cycles can push overall
power cycle efficiency to nearly 60%. Overall energy use can substantially exceed even
(1)
this when electrical generation is combined with process steam use. Table 1-1 shows a
sample of the increased cycle efficiencies and heat rates thought to be possible in the
early 1990s.
Table 1-1
Sample Cycle Efficiencies and Heat Rates
System
Efficiency, %
Heat Rate, Btu/kWh (J/Wh)
Simple gas turbine
32
10,700 (11,286)
Gas turbine plus unfired single

pressure steam cycle
42
8,200 (8,649)
Advanced gas turbine plus

unfired multiple pressure
steam system
48
7,100 (7,489)
Gas turbine plus dual pressure

steam system plus process
steam use (cogeneration)
61
Note: All values are calculated using the higher heating value (HHV) of the fuel. Use of the
lower heating value (LHV) of the fuel would increase the efficiencies listed.
1-1

Introduction
Design improvements have further increased cycle efficiencies. Currently, gas turbine
efficiencies of 40% and greater are attainable with steam turbines capable of 46%
efficient operation. Use of such a gas turbine in a combined cycle (single pressure
steam system) would raise overall efficiency to about 50% or greater. Efficiencies of
more complex designs (advanced gas turbine/multipressure steam systems) are at 58%
and expected to reach 60%. The efficiency of cogeneration facilities is variable,
depending on the relative amounts of steam applied for power generation and process
use, and the extent of condensate return to the cycle, but are also capable of operating
at around 50% efficiency.
Changes in the energy market place have also been favorable to this technology.
Competition to sell power at the lowest profitable price have placed premiums on
designs which offer the following features:
high efficiency
quick response peaking service capability
low operating costs (manpower, fuel)
reduced emission of greenhouse effect gases such as CO2
Waste heat units provide all of these capabilities, resulting in substantial advantages
over conventional fossil plants.
1.2 TYPES OF CYCLES AND STEAM GENERATORS

Figure 1-1(1) shows a simplified combined cycle system schematic.
Figures 1-2 and 1-3 show simplified diagrams of natural circulation and forced
circulation Heat Recovery Steam Generators (HRSGs), while Figure 1-4 shows a more
complex arrangement of a natural circulation unit.(2)
Figure 1-5 illustrates the key differences between vertical tube and horizontal tube
designs(20).
1-2

Introduction
Heat recovery
steam generator
Flue gas
Bypass
flue gas
outlet
Fuel
Stack
Air
Electricity
Supplemental
fuel (optional)
Gas to HRSG
Gas turbine-generator
ter
dwa
Fee
Electricity
d
eate
stea
erh
Sup
Pump
Steam
turbine-generator
Condenser
Pump
Deaerator
and storage
Exhaust
flue gas
Combustor
Fuel
Steam
turbine-generator
Superheated steam
Bypass
Air
Stack
Electricity
Electricity
Flue
gas
Compressor
Turbine
Gas turbine-generator
Heat recovery
steam generator
Feedwater
Condenser
Supplemental
fuel
Pump
Pump
Deaerator
and storage
Figure 1-1
Simplified combined cycle system schematics.(1)
1-3

Introduction
Feedwater
inlet
Steam outlet
Stack
Drum
Gas
turbine
exhaust
Superheater
Evaporator
Economizer
Figure 1-2
Natural Circulation, vertical tubed, single pressure HRSG(2)
Feedwater inlet
Economizer
Evaporator
Drum
Superheater
Gas
turbine
exhaust
Pump
Steam outlet
Figure 1-3
Forced Circulation, horizontal tubed, single pressure HRSG(2)
1-4
To LP turbine
Condensate makeup
For Reheater
To LP
suhtr
HP steam
Feedwtr Prehtr
HP Econ
IP Econ
HP Econ
IP Evap
HP Econ
LP Suhtr
LP Evap
LP
Drum
IP
Drum
IP Suhtr
SCR
HP Evap
DA
IP steam
HP
Drum
HP Suhtr
To HP turbine
Reheat steam from HP turbine
Reheater
Reheater
Supplementary
fired duct burner
HP Suhtr
To IP turbine
To GT injector
To condenser
Introduction
Gas turbine
exhaust
Attemperator spray
Figure 1-4
Natural circulation, horizontal tubed, multi-pressure HRSG(2)
1-5

Introduction
Vertical Design
LP drum
HP Drum
Feedwater
storage tank
Preheater
LP Evaporator
LP Superheater
HP Economizer
HP Evaporator
HP Superheater
Horizontal Design
Feedwater storage tank
LP drum
HP drum
HP Superheater
HP Evaporator
HP Economizer
Preheater
LP Evaporator
LP Superheater
Figure 1-5
Horizontal and vertical tube typical configurations for drum-type HRSGs(20)
1-6

Introduction
The general range of current HRSG parameters is shown in Table 1-2. (1) Further
general pressure ranges for HRSGs are shown in Figure 1-15.
Table 1-2(1)
HRSG Parameters
Turbine application:
Gas turbine sizes
1 MW to 220 MW*
Gas flow
25,000 to 5,000,000 lb/h (0.32 to 630 kg/s)
Gas turbine outlet temperature
1200F ( 649C)
Supplemental firing temperature
1650F ( 899C)
Steam flow:
15,000 to 1,000,000 lb/h (1.9 to 127 kg/s)
Operating pressures:
High
2000 psig (138 bar)
Intermediate
50 to 400 psig (3.4 to 28 bar gauge)
Low
15 to 50 psig (1.03 to 3.4 bar gauge)
Steam temperature
up to 1005F (541C)
Supplemental fuels
#2 oil, natural gas
*Higher capacity gas turbines are now available and in use.

(1)
The general temperature and cycle efficiency profile is shown in Figure 1-6 of natural
circulation single pressure HRSGs.
Figure 1-7 shows a once-through steam generator (OTSG) flow schematic.(3) This cycle
is very simplified and consists of a once-through HRSG having a LP section fed by the
LP boiler feed pump, and an HP section fed by an HP feed pump, which takes suction
from the LP feed pump discharge. Both the LP steam and HP steam feed a condensing
steam turbine. Although not shown, part of the LP steam could be used for
cogeneration purposes. Also in more advanced cycles, reheat would be added. Several
small systems such as shown in Figure 1-7 have been installed at a number of sites in
the US and Canada and have operated very reliably on oxygenated treatment.
More complex combined cycle units have been designed and are under construction
which consist of a once-through HRSG and a one or two drum HRSGs. Such a system
was introduced recently(13) and is shown schematically in Figure 1-8. The water
treatment consists of AVT for the LP drum HRSG and oxygenated treatment (OT) for
the HP once-through HRSG. The design also includes an HP water/steam separator in
lieu of a condensate polisher. Units with this combination of drum and once-through
HRSGs have improved efficiency. The low pressure drum HRSG provides water for
the high pressure once-through HRSG.
Another concept under construction consists of IP and HP once-through HRSGs and LP
drum boiler. The designed water treatment is AVT with elevated pH for the LP boiler,
1-7

Introduction
and oxygenated treatment for the IP and HP boilers. The plant is equipped with a fullflow condensate polisher.
Temperature, F (C)
Superheater approach, TSH

TGi
1000
(538)
TFO
TGO
Turb
i
TFO
ne e
St
800
(427)
TGI
xhau
st ga
ea
m
TFI
600
(316)
Pinch point, TP
TSat
Economizer approach, TE
400
(204)
Fe
ed
wa
te
200
(93)
Superheater
0
20
Evaporator
40
60
Heat Recovery Fraction (%)
Figure 1-6
Temperature profile in single pressure HRSG(1).
1-8
Stack
temperature
TGO
Feedwater
inlet
temperature
Economizer
80
TFI
100

Introduction
Flu gas to stack

Once-through heat recovery steam generator
LP section
LP steam
HP section
HP steam
Steam
turbine
Flue gas
Electricity
Condenser
Condensate
storage
Makeup
system
Bypass
Combustion
turbine and
generator
Air
Fuel
H.P. boiler feed
Condensate
polisher
L.P. boiler
feed pump
Figure 1-7
Once-through combustion turbine combined cycle(11,12)
1-9

Introduction
GT air cooler
Blow
down
G
Natural gas
Figure 1-8
Combination drum and once-through HRSG(13)
1-10

Introduction
1.3 MATERIALS
For economic reasons the majority of the materials currently used in the construction of
HRSGs is carbon steel. They are classified by their carbon content and are used for
tubing, drums, casings and ducts. Temperature limitations are influenced by the
carbon content. Low carbon steels are limited to about 800F (427C) and high carbon
steels to about 1000F (538C) due to potential oxidation. Some manufacturers go to
low chromium steels above 800F (427C). Exceptions to this are certain OTSGs which
currently utilize Alloy 800 (a nickel-chromium austenitic steel) in their tubular steam
(3)
generating banks.
Components operating above 950F (510C) require alloy steels that are characterized
by their chromium content. Of the alloy steels, Grade 91 (9Cr-1Mo-V) is the highest
available and can be used to 1200F (649C). The practical limit is closer to 1100F
(593C) due to low strength above this temperature. At higher temperatures, austenitic
stainless steels are required.
Carbon steel is usually applied in the economizer and evaporator sections with some
operators requesting T-11 and T-22. These grades as well as carbon steel and T-91 can
be utilized in superheaters and reheaters. Preheaters (if utilized) are typically made of
either stainless steel (such as T-430) or carbon steel.
HRSG designers frequently specify finned tubes to increase heat transfer. This makes
the circuits more compact and difficult to access.
1.4 HEATING SURFACE

Figure 1-9 shows the approximate surface required in convection tube banks and
vestibule for various entering and leaving gas temperatures for natural circulation
boilers. This type of information will be required in developing the optimum HRSG
drum boiler water treatment in Section 9 (Figure 9-5).
1.5 WATER QUALITY AND QUANTITY CONSIDERATIONS

There are several differences between combined cycles and conventional power plant
cycles. Water treatment practices for combined cycles, therefore, require that certain
considerations be reviewed, which in many cases were not a factor when designing
water treatment facilities for conventional units. This subsection will focus on these
differences in characteristics of combined cycles and their effects on water treatment,
and water and steam cycle chemistry. The next subsection outlines the possible
chemistry treatments for HRSGs.
1-11

Introduction
Convection Heating Surface

ft2/1000 lb Gas (m2/1000 kg)
125
(25.6)
100
(20.5)
A
Gas
temp
75
(15.4)
650F
(343C
750F
50
(10.2)
25
(5.1)
88C
0F (2
g, 55
vin
. lea
(399C
For
Gas Mass Velocity
m/A = 2000 lb/h ft2 (2.712 kg/m2s)
Convection Heating Surface

ft2/1000 lb Gas (m2/1000 kg)
100
(20.5)
75
(15.4)
B
Gas
650F
25
(5.1)
C)
(288
(343C
750F
(399C
For
Gas Mass Velocity
m/A = 3000 lb/h ft2 (4.068 kg/m2s)
0
1000
(538)
1200
(649)
40
(8.2)
Vestibule Heating Surface
ft2/1000 lb Gas (m2/1000 kg)
550F
. le
temp
50
(10.2)
C
30
(6.1)
g,
avin
Conditions for diagrams A & B

Tubes 2.5 in. (63.5 mm) OD in-line
Tube spacing ll and lll = 5 in. (127 mm)
Sat. temperature Tsat = 450F (232C)
Draft loss, 0.2 to 0.4 inc. wg
(0.05 to 0.1 kPa)
1400
1600
1800
2000
(760)
(871)
(982)
(1093)
Gas Temperature Entering, F(C)
Sat. temp.
Tsat = 450F (232C)
2200
(1204)
)
49C
F (6
200
1
,
g
avin
p. le
tem
s
a
G
C)
760
0F (
20
(4.1)
140
C)
871
0F (
160
10
(2)
C)
982
0F (
180
1400
(760)
1600
(871)
1800
(982)
2000
(1093)
3C)
109
0F (
200
0
1200
(649)
2400
(1316)
2200
(1204)
2400
(1316)
Gas Temperature Entering Water-Cooled Vestibule, F (C)
Figure 1-9
Approximate surface required in convection tube bank and vestibule for various
entering and leaving waste gas temperatures.
1-12

Introduction
Three aspects materially affect the selection of the chemistry, the makeup quantity and
quality for combined cycles:
Multiple pressure drum HRSGs
Cogeneration requirements, and
Use of water or steam for control of nitrogen oxide (NOx) emissions
Multiple Pressure Drum HRSGs

As indicated in Section 1.2, numerous HRSG designs exist and others are being
developed. Drum units which operate at two or more pressures pose special challenges
for personnel responsible for chemistry. Treatment selection becomes more
complicated; the optimum chemistry may be different for individual pressure stages.
As a consequence of this, it may be necessary to seek a compromise between pressure
stages. During the selection process, there is a need to consider the system as a whole,
paying close attention to interactions of treatments to be applied in different parts of
the system. Selection of an appropriate treatment for each drum HRSG circuit is
discussed in detail in Section 9 of this report; optimization of the selected treatment is
covered in each of the chemistry sections (3 for phosphate, 4 for AVT, 6 for CT and 7 for
OT).
As an example, it has been observed that hydrazine tends to build up in the lower
pressure circuits of multiple pressure drum HRSGs. Provision of individual dosing
systems to inject hydrazine to the suction side of each feed pump has been practiced to
avoid this problem on certain units.
Cascading of blowdown is widely practiced in multiple pressure drum HRSGs because
of the efficiency improvements associated with this technique. The interactions
resulting from cascade blowdown must be factored into selection and control of water
treatment. Some HRSG bid specifications have limited blowdown to 1% of drum steam
flow (with any excess blowdown required sent to waste). In the absence of such
limitations, all blowdown from the HRSG HP circuit may be directed to the LP or IP
circuit; increasing cation conductivities in the IP or LP boiler water have then to be
considered.
Cascading is only effective with continuous blowdown operation. If the blowdown is
operated based on boiler water analysis, the benefits may be negligible. Such
intermittent blowdown philosophy is usual on European HRSG designs.
1-13

Introduction
Cogeneration
Cogeneration potential is a common reason for installing both simple combustion
turbine cycles and combustion turbine/combined cycles. Both make use of heat
recovery steam generators (HRSGs) to supply steam.
In the case of the simple combustion turbine cycle, steam is produced for the exclusive
use of district heating or for an industrial process (refining, paper mill, etc.). Any
electricity produced may also be used in the industrial process and/or fed into a utility
grid system. Makeup water requirements can range up to 100%, depending upon the
amount of condensate returned from the industrial facility.
The combined cycle requires that steam be available for the steam turbine, which
reduces the amount available for cogeneration purposes. The electricity produced
would be used in a manner similar to the simple cycle. Makeup requirements are again
dependent upon the quantity of condensate returned from the industrial facility.
However, since the steam from the steam turbine is condensed and reused in the cycle,
makeup requirements would be considerably less than 100%.
The quality of condensate returned from the cogeneration operation is subject to
contamination, sometimes severe. Contamination can include oils, chemicals and solid
materials, all of which can adversely affect operation of the steam generation systems, if
not removed. Sampling for total organic carbon (TOC) will detect organic chemical
contamination, including oils, while continuous conductivity measurements will detect
inorganic chemical contamination, such as acids or alkalis. When these contaminants
are detected above pre-established limits, the condensate should be discarded to waste.
As a minimum, it is advisable that the remaining condensate (low in TOC and
conductivity) should be filtered prior to use in the cycle to remove extraneous solid
materials.
Nitrogen Oxide (NOx) Control in Gas Turbines

Many combustion turbines require large quantities of water or steam to reduce NOx
emissions (and/or to increase power output of the combustion turbine/generator).
This requirement has, however, been eliminated on many recent combustion turbines
when firing natural gas. Some oil fired combustion turbines also may have dry NO x
control. The water or steam must be sufficiently pure to prevent deposition on, and
corrosion of, the combustion turbine.
Limits for water or steam used for NOx control from various combustion turbine
manufacturers can be found in Appendix A. The sodium and potassium limits(5) are
quite stringent because compounds of sodium and potassium are very corrosive to
combustion turbine components. These same limits are also prescribed for sodium and
1-14

Introduction
potassium in the fuel used to supply the combustion turbine. Because the quantity of
water or steam injected into the combustor can be greater than the quantity of fuel
used, the maximum levels established for sodium and potassium in the steam or water
are such that the sum of contaminants does not exceed the maximum level permitted in
the fuel alone. Some manufacturers(5) recommend that the normal level should not be
exceeded when burning oil; however, the maximum levels are permitted when burning
gas.
(5)
Maximum levels have also been established for heavy metals , although their levels
would be expected to be low if sodium and potassium limits have been met.
Silica, magnesium and calcium, while not corrosive, can significantly increase gas
turbine blade fouling. Generally, the quality of injected steam or water should be
largely the same as for the quality of steam required by a steam turbine (5).
Attemperation for Steam Turbines

As is the case with conventional units, superheated and reheated steam requires
attemperation to control temperature in a satisfactory manner. The water used for this
purpose must approach or equal the quality of the steam required at the steam turbine
inlet. Therefore, the contaminants entering the steam from the attemperation water
when mixed with the contaminants in the superheated and reheated steam cannot
exceed the limits established for the steam to the steam turbine inlet.
Certain combined cycle designs utilize low pressure (LP) evaporator sections that are
integral deaerators, as further described later. With these designs, the attemperation
water is furnished from the LP section. This precludes the use of solids based nonvolatile treatments (phosphate or caustic) for the LP system, since the phosphate or
caustic would contaminate the superheated or reheated steam. This design necessitates
the use of all-volatile treatment (AVT) or oxygenated treatment (OT) in the LP section
to prevent contamination of steam to the steam turbine.
Solids based treatments could be applied in higher pressure circuits, providing no
blowdown is directed to the LP section.
Should a situation exist where solids-based treatment of the LP system appears
necessary, consideration should be given to alternative attemperation water sources or
methods. For example, it may be possible to employ LP feedwater, condensate or
treated makeup for spray attemperation. Attemperation by means of a heat exchanger
(sweetwater condenser) would allow use of solids-treated water for attemperation
without contamination of the steam.
1-15

Introduction
Reducing Agent (Oxygen Scavenger) Usage

Condensate preheaters and feedwater heaters are generally either stainless steel or
carbon steel. The only copper alloys in the cycle might be for the condenser tubes.
Therefore, the use of hydrazine or other reducing agents can be minimized or possibly
eliminated(6), depending on the water purity, which should reduce the potential for
flow-accelerated corrosion (FAC). Many utilities have operated conventional units
without any reducing agent in all-ferrous cycles and high purity water with very
satisfactory results(7,8).
If the cogeneration partner is using steam for any food preparation processes, the use of
hydrazine is strictly prohibited, as are many other corrosion control additives. Steam
additives for such applications must be approved by the Federal Food and Drug
Administration.
1.6 COMBINED CYCLE/HRSG CHEMISTRY TREATMENTS

Section 9 of these guidelines provides road maps for the selection and optimization of
the boiler water and feedwater chemistry for HRSGs. This should be the first section to
be reviewed in selecting the chemistry for new HRSGs or for optimizing or changing
the current chemistry. This subsection provides brief overviews of the possible
chemistry choices and directions to the appropriate guideline section.
Phosphate Treatment Applicability

Phosphate treatments of various types are the most common form of corrosion
protection for drum-type HRSGs in use with combined cycles in operation today.
However, there appears to be a lack of uniformity or agreement on the control limits for
key parameters (pH, phosphate concentration, sodium to phosphate ratio) in those
units operating with this boiler treatment philosophy. There also seems to be a
mistaken belief that, because many of the HRSGs operate at low pressure, that proper
boiler water chemistry control is unimportant. Section 3, Cycles with Drum HRSGs on
Phosphate Treatment, presents guidance on how to establish an optimum phosphate
treatment program and recommends limits for water chemistry parameters throughout
the entire heat cycle. Two phosphate treatments are included: equilibrium phosphate
treatment (EPT) and phosphate treatment (PT). Congruent phosphate treatment (CPT)
is not included because of the possibility of acid phosphate corrosion failures.
Phosphate treatment cannot be applied to once-through units for obvious reasons.
Also, as previously mentioned, phosphate treatment cannot be applied to those low
pressure drum boilers which furnish water for steam attemperation.
1-16

Introduction
All-Volatile Treatment (AVT) Applicability

All-volatile treatment (AVT) can be used in both once-through and drum-type HRSGs.
There have been many reports of severe flow-accelerated corrosion (FAC) in tight
radius control bends of horizontal evaporator tubes within those HRSGs operating on
AVT (see Section 1.10). The use of excessive hydrazine or other oxygen scavengers
(reducing agents) in the pre-HRSG circuits may be responsible for the many FAC
failures reported in such units. The lack of copper alloys in combined cycles (except
perhaps for the condenser) permits reducing agent levels to be minimized, or, in many
cases eliminated.
Section 4, Cycles with Drum HRSGs on All-Volatile Treatment, and Section 5,
Cycles with Once-Through HRSGs on All-Volatile Treatment, present guidance on
optimizing AVT for drum and once-through units. In addition, limits are given for
water chemistry parameters throughout the entire heat cycle.
Caustic Treatment Applicability

Caustic treatment (CT) is most applicable in instances where phosphate chemistry
approaches have been evaluated and found to be unsatisfactory (Section 9.5), or where
severe FAC has been found in the lower pressure circuits. CT should be considered in
applications where there is a significant risk of cycle contamination (condenser leaks,
condensate returns) such that all-volatile and oxygenated treatments cannot be used.
As with phosphate chemistry, CT cannot be used in once-through units and care must
be taken to avoid dryout in drum units. Carryover from all drums must be monitored
carefully; this is to avoid introduction of sodium hydroxide to the turbine. Section 6 of
these guidelines provides information on the use of CT in HRSG drum boilers.
Oxygenated Treatment (OT) Applicability

Worldwide, there are many conventional units, both once-through and drum units,
operating on OT. There is no reason why OT can not be applied to HRSGs, if water
quality and materials of construction (no copper except possibly in the condenser) are
suitable. The use of high purity water is considered mandatory for optimum results
with OT. Condensate polishing is the usual means for achieving the desired purity, but
not the only one (see Section 1.7).
By far the most widely used HRSGs worldwide are of the drum type, and nearly all
have no condensate polishing. For those units to apply OT, condensate polishing
would have to be back-fitted. New installations should, of course, be designed with
condensate polishers initially.
1-17

Introduction
As already indicated in Section 1-2, several smaller size once-through units have been
installed in the US and Canada(11,12) which feature once-through designs which
essentially operate on OT, since no deaeration is provided (Figure 1-7). The oxygen
content is uncontrolled, but apparently is generally within the limits prescribed for OT.
These units feature condensate polishing and Incolloy 800 in the HRSG. A larger
combined cycle unit of this type was recently installed(11).
An advanced combined cycle power plant was recently described(13) which features a
HRSG with a low pressure (LP) drum boiler and a high pressure (HP) once-through
boiler (Figure 1-8). The LP boiler uses AVT whereas the HP boiler uses OT. No
condensate polishing is provided. High purity water is maintained through the use of
a HP Water Separator installed between the evaporator and superheater, acting as an
intermittent blowdown. A number of these advanced combined cycles are now being
constructed and due for commissioning in late 1999 or early 2000.
Section 7, Cycles with Drum HRSGs on Oxygenated Treatment, and Section 8,
Cycles with Once-Through Units on Oxygenated Treatment, present guidance on
optimizing OT for drum and once-through units. In addition, limits are given for water
chemistry parameters throughout the entire heat cycle.
1.7 BALANCE OF PLANT

Some aspects of the balance of plant for combined cycles are similar to conventional
cycles. Examples of these similarities would include the steam condenser and water
makeup system. Examples of differences would include feedwater deaeration and
feedwater heating.
This sub-section will focus primarily on the differences in characteristics of combined
cycles and their effects on power plant design, water quality and operations.
Deaeration
As with conventional cycles, deaeration can be accomplished in the condenser and/or
in a separate deaerator. There are also low pressure (LP) evaporators that are integral
deaerators.(9,14) The steam circulation loop of the LP evaporator section is through the
feedwater storage tank of the deaerating heater. As previously mentioned, this
arrangement precludes the use of phosphate treatment, since attemperator spray water
would come from the integral storage tank.
A once-through HRSG design installed in several locations in the US and Canada
utilizes no deaerator(11) and essentially operates on OT. Any deaeration that does occur
takes place in the air removal section of the condenser. Condensate dissolved oxygen
levels in this cycle coincide with typical condenser specifications at 40 ppb.(11)
1-18

Introduction
Feedwater Heating
Low pressure feedwater heaters are seldom included in combined cycle power plants.
One reason for this is that the allowable economizer inlet temperature can be low
(natural gas operation). Also, if some feedwater preheating is required, pegging steam
from the HRSG can be used. If a feedwater preheater is included in the cycle and
oxygen levels are anticipated to be high, the preheater may be fabricated with a ferritic
stainless steel (Type 430).(5) Other materials mentioned as being used for preheaters
(9)
include 304, 2205 or even carbon steel.
Since the heat cycle for combined cycles are all-ferrous in nature (except perhaps for the
steam condenser), no compromise need be made in the matter of pH control as
required for mixed-metallurgy cycles. Also with proper water chemistry, such systems
are amenable to OT as well as AVT, and lend themselves to minimal reducing agent
(oxygen scavenger) concentrations, or to possible elimination.
Makeup Requirements
Makeup requirements for cycles with HRSGs can be significantly greater than the
requirements for conventional cycles, ranging from almost 0 to 100% of steam flow.
Factors affecting makeup include the following:
Type of cycle
Cogeneration requirements/quantity of returned condensate
Necessity for water or steam injection into the combustion turbine for NOx control
(and/or to increase power output of the combustion turbine/generator)
Blowdown and other cycle losses (leakage, steam seals, water and steam sampling,
etc.)
The water quality required for these cycles depends upon several factors, such as:
Requirements for water or steam injection for NOx control
Attemperation water source and quantity
Amount of makeup in relation to condensate flow
Amount and quality of condensate return in relation to condensate flow
Design of HRSG (once-through or drum-type)
1-19

Introduction
Even though the drum-type HRSGs may operate at relatively low pressures (relative to
conventional units) the above factors will dictate that the makeup system furnish a
quality of water approaching (or equaling) that produced from a mixed-bed unit. The
once-through HRSGs dictate that mixed-bed quality water be provided for makeup.
Water quality considerations from HRSG manufacturers may be found in Appendix A.
Water quality recommendations established in these Guidelines are given in Sections 3
through 8, depending upon the chemical treatment methods used in the HRSG and
heat cycle.
It should be understood that the importance of makeup purity control is particularly
acute in units with high makeup requirements. Clearly, the influence of sodium or
silica leakage on condensate, feedwater and boiler water chemistry will be more
significant in cases where makeup represents more than 50% of feedwater flow than it
will in instances where makeup is less than 10% of feedwater flow. Total organic
carbon may be of special concern in units with high makeup requirements since ion
exchange is less efficient in removal of organic impurities than in removing inorganics.
Organic deposition on ion exchange resins reduce their exchange capacity and limit
regeneration capabilities. Breakdown of organic impurities will result in creation of
acetate and formate which can depress boiler water pH and increase cation
conductivity levels in the cycle.
Condensate Polishing
The use of condensate polishing is rare for existing units featuring drum-type HRSGs.
However, the dearth of condensate polishing on these existing units cannot be used as
evidence that polishing would not improve water chemistry or that polishing might not
even be required in certain circumstances.
Condensate polishing has proven to be cost justified for conventional drum type units
in recent EPRI studies(15) based upon consideration of the following factors:
Mitigation of condenser leakage (especially on high solids cooling water such as

from closed cycles or sea water)
Improvement in startup time
Reduction in boiler blowdown
Reduction in the need for chemical cleaning
Reduction in boiler tube failures
1-20

Introduction
There is no reason to believe that the above considerations would not be equally
applicable to drum type HRSGs for combined cycles or even simple cycles (with the
exception of benefits attributable to condenser leakage).
Condensate polishing is required for once-through HRSGs and for drum-type HRSGs
operating on OT. An exception to this requirement has been taken in the latest
advanced cycles which combine a drum-type and once-through HRSG in the same
unit(13) (Figure 1-8).
The once-through HRSG design installed in several locations in the US and Canada(11)
uses non-regenerable mixed-bed polishers which have very low makeup requirements.
Condensate polisher resins are replaced when exhausted, and not regenerated. A full
flow filter is placed downstream of the polisher. No chemical feed is used in the heat
cycle, which essentially operates on OT.
Condenser
Both water cooled and air cooled designs have been used. For the former, tube
materials would be a function of type of raw water in the circulating water system and
may include copper alloys, stainless steels or titanium. To preclude copper deposition
in the HRSG and steam turbine, recommendations for condenser tubes would include
the use of stainless steels or titanium, as applicable. Higher iron levels are usually
found in feedwater with air-cooled condensers (see Section 1.11).
1.8 CHEMICAL CLEANING

Because HRSGs normally have feedwaters that have not been exposed to extensive preboiler piping and heat exchangers, it was believed that accumulation of corrosion
product oxides on the steam generating water-side surfaces would be slow in forming,
and in conjunction with low heat absorption rates would not lead to tube metal
overheating.
While this contention is largely true, there is still the problem of under-deposit
corrosion associated with soluble (and corrosive) feedwater contaminants along with
possible corrosive attack from water treatment chemicals (typical occurrences are acid
phosphate or caustic corrosion beneath oxide deposits). These issues are a major
concern for extended operation. Failures of HRSG tubing are discussed later in Section
1.10.
References 16 and 17 for chemical cleaning contain the accumulated data for cleaning
utility fossil steam generators. It is believed that HRSGs will have to be chemically
cleaned during their service life. The referenced material addresses the methodology
for chemical cleaning, the chemical solutions utilized and the technology of their safe
1-21

Introduction
disposal. Figure 1-10 shows the allowable accumulation of deposits in conventional

fossil boiler steam generating tubes as a function of system pressure. In the absence of
other available data, these deposition limits are suggested as current guidelines for
operational chemical cleaning of HRSGs over the range of pressures to which Figure 110 applies.
Operational chemical cleaning may also be considered under other circumstances,
including the following:
experience of contamination causing, or potentially a precursor to, underdeposit

corrosion and HRSG tube failures
change in cycle chemistry treatment
installation and/or change in auxiliary firing equipment or fuel (where applicable)
after incomplete or improper chemical cleaning
after extended idle periods, if inspections reveals layup method was ineffective
(resulting in corrosion)
Note that the final two items involve inspection of waterside surfaces, possibly
supplemented by collection of one or more HRSG tube samples. A similar approach
should be taken with respect to preoperational cleaning of new equipment. The
cleaning requirements of the supplier assume a reasonable standard of care was taken
during shipment and storage of tubes. However, they cannot cover all scenarios which
may develop during construction. Actual cleaning requirements need to consider field
storage (corrosion, dust and dirt) conditions. Further contamination of the waterside
surfaces may occur during assembly of field erected units.
1.9 CHEMISTRY PROBLEMS IN HRSG UNITS

The extent of chemistry problems which have developed at HRSG facilities around the
world was the primary motivation to develop these guidelines. HRSG tube failures
have been experienced, which are attributable to flow-accelerated corrosion (FAC),
corrosion fatigue, and underdeposit corrosion, including hydrogen damage, caustic
gouging and acid phosphate corrosion. Carryover of solids from drum HRSG units has
resulted in deposition and corrosion in turbines, including stress corrosion cracking by
caustic. Pitting corrosion due to oxygen ingress during shutdown is also a concern.
Fouling of boiler flow distribution orifices can lead to uneven flow over the steam
generator tubes.
Design and operating criteria applicable to these units increase their susceptibility to
chemistry-related damage. HRSGs tend to be very compact and sometimes employ
1-22

Introduction
horizontal tube arrangements. Horizontal tubes in LP service are particularly prone to

FAC, while IP and HP tubes are subject to steam blanketing and dryout. Although heat
fluxes are generally well below those present in conventional boilers, use of auxiliary
fuels and firing equipment (duct burners) can create localized variations in heat
distribution. Both natural and forced circulation designs are in use. The units are
capable of rapid startup and shutdown, which makes them well suited to peaking
operation. However, this type of service increases the probability of thermal fatigue
problems, corrosion fatigue damage, and may result in ineffective circulation, creating
the opportunity for underdeposit corrosion activity. In many instances, chemistry
programs in effect at HRSG facilities do not address protection of equipment during
shutdowns and idle periods.
1-23

Introduction
Specific Deposti Weight, g/ft2

60
Deposit Weight by Mechanical Method
50
Cleaning required
40
30
20
Consider cleaning
10
No cleaning required
0
1.5
1.9
2.3
2.7
Pressure, psig x
103
Specific Deposti Weight, g/ft2

60
3.1
3.5
Metric conversions
g/ft2 x 1.07 = mg/cm2
psig x 6.9 x 10--3 = MPa
Deposit Weight by Solvent Method

50
Cleaning required
40
30
Consider cleaning
20
10
No cleaning required
0
1.5
1.9
2.3
Pressure, psig x
2.7
3.1
103
Figure 1-10
Permissible Specific Deposit Weight Limits As A Function of Boiler Pressure for
Conventional Fossil Plants(17)
1-24
3.5

Introduction
Carryover and Turbine Damage

Although rates of mechanical and, especially, vaporous carryover increase with drum
pressure, experience has shown that any stage of a multiple pressure drum HRSG may
be subject to carryover. Drum swell at startup has been observed to result in carryover
from the LP circuit(18). As part of chemistry activities to be addressed during unit
commissioning, carryover rates for each drum should be measured to verify
compliance with specifications and suitability of chemical treatment and operating
practices. This step is key in the selection of the optimum boiler water treatment
(Section 9).
Impurities introduced to the turbine with the steam tend to form deposits and may
initiate pitting corrosion and stress cracking. Carryover of sodium hydroxide has been
noted to result in stress corrosion cracking damage of steam turbines at HRSG facilities,
as well as in conventional fossil plants(21). Carryover of chlorides, sulfates and organics
are also known to increase corrosion within the turbine.
Other species which may be present in the steam tend to form deposits which will
reduce steam turbine efficiency. Volatilization (of primary concern at elevated drum
pressures) can result in carryover of silica (which can deposit in the LP turbine) and
copper (if present, which can deposit in the HP turbine). Mechanical carryover will
introduce any solids present in the boiler water to the steam path. When solids-based
treatments are in use, sodium phosphates (which form deposits in the HP turbine) and
sodium hydroxide (stress corrosion cracking) will be transported by mechanical
carryover from the drum.
Corrosion During HRSG Unit Shutdown and Idle Periods

In the absence of effective shutdown and layup procedures, dissolved oxygen will enter
the system as it is removed from service. As mentioned in the discussion of HRSG tube
failures, peaking operation greatly increases the probability of corrosion fatigue
damage. An additional concern associated with air ingress is the development of
pitting corrosion of carbon steel throughout the system, as well as general corrosion of
any copper alloys which may be present.
Avoidance of corrosion during idle periods involves either exclusion of oxygen and/or
moisture from the system. This can be accomplished by several techniques including:
Maintaining condenser vacuum
Keeping water above boiling temperature
Use of steam blankets, coils and spargers

1-25

Introduction
Use of nitrogen blanketing
Use of chemical treatment (wet layup)
Use of dehumidified air (dry layup)
Selection of the most appropriate shutdown procedures and layup methodologies is

highly specific to unit design and operating criteria. General guidelines for layup of
HRSG units are provided in Section 10 of this report.
1.10 HRSG TUBE FAILURES

In conventional fossil plants, the mechanisms and root causes of boiler tube failures
(BTF) are well understood(19), particularly those that are influenced by the boiler
chemistry choice and the purity. The HRSG/combined cycle is a relatively new
generation source and thus it is quite surprising that so many of the well understood
failure mechanisms in conventional plants have already started to occur in HRSG
tubing.
The purpose of this subsection is simply to delineate some of these HRSG tube failures.
The reader is also referenced to Section 9.1 where some other chemistry control
problems are discussed. The clear message here is that sufficient technical
consideration has not been given to feedwater and boiler water chemistry choices in
influencing HRSG failure mechanisms. It is hoped that the proper selection and
optimization of cycle chemistry for HRSG units, described in Section 9, will be a first
step in addressing current or future failure mechanisms. Further, it is hoped that the
development of cycle chemistry guidelines as indicated in Sections 38 will be the
second and continuing step to ensure that such failures will not occur.
Flow-Accelerated Corrosion (FAC) in HRSG Evaporator Tubing

Probably this mechanism is the most prolific and common failure mechanism in low
pressure HRSG tubing. Figure 1-11 shows a typical example of a failed HRSG tube
bend from a LP circuit. The LP circuit was operated on AVT with a reducing agent
supplied to the feedwater. Hydrazine is the most common reducing agent, but failures
have occurred with a wide range of agents including hydroquinone and ascorbic acid.
FAC has also been experienced in LP HRSGs where the boiler water treatment included
organic polymers. For combined cycles, organic based treatments are generally not
necessary, and therefore have not been considered in the discussions on boiler water
treatments in the previous sections of this guideline. If the use of these treatments is
considered, then the effects of decomposition products such as organic acids, carbon
dioxide, etc. should be properly assessed.
1-26

Introduction
Figure 1-12 shows a detail inside that tube, which clearly indicates the FAC failure
appearance and shows the characteristic chevron markings of FAC. Metallographic
cross-sections through this region reveal no evidence of any protective magnetite on the
tube surface. Another interesting feature is the area of what appears to be excessive
deposition about 2 in. (5 cm) from the FAC area. However, on cross-section this
appears to be a new form of magnetite, which has been called box-like. It appears
this may be an indicator of two phase flow and/or local boiling, and could be used as
an early sign of FAC in HRSG tubing. Similar phenomena have been seen in a number
of HRSG tubes suffering FAC; the superficial appearance is one of blisters on the tube
surface.
Under-Deposit Corrosion in HRSG Evaporator Tubing

Acid Phosphate Corrosion. Conventional plants operating on congruent phosphate
treatment (CPT), experiencing hideout, and with additions of low molar ratio
phosphate chemicals, have experienced an under-deposit corrosion mechanism called
acid phosphate corrosion (APC)(19). Figure 1-13 shows typical APC in an HRSG high
pressure (1500 psi, 10.3 MPa) tube, which was operated on CPT and with additions of
phosphate down to Na:PO4 molar ratios of 2. Analyses of the severely corroded areas
reveal that maricite (the NaFePO4 corrosion product typical of APC) is present.
Caustic Gouging. This is another conventional plant failure mechanism which occurs
when excess of sodium hydroxide (> 2 ppm) has been added to high heat flux boilers,
or where sodium hydroxide has been added to AVT boilers in times of
contamination(19). Caustic gouging has also been reported in HRSG evaporator
(20)
tubing .
Corrosion Fatigue
HRSG tubing and header circuits can be subjected to severe thermal cycles which were
not considered in the design(18). Figure 1-14 shows typical incipient corrosion fatigue
damage in HRSG economizer tubing after only about 4000 hours. The cracks are
initiated from the waterside, are circumferentially oriented, and transgranular with
oxide lobes along the crack face. These features are very typical of corrosion fatigue in
(19)
waterwall and economizer tubing of conventional plants ; they always occur at
regions either where the thermal expansion is restrained or where there is an external
attachment. It is now reasonably well understood that the strain on the inside surface
has to be greater than 0.2% to crack the protective magnetite and that both phosphate
treatments and AVT can influence the rate of propagation if wide pH swings are
experienced.
1-27

Introduction
Figure 1-11
Flow-accelerated corrosion at the bend of a low pressure HRSG evaporator tube.
1-28

Introduction
Figure 1-12
Detail of the FAC shown in Figure 1-11. Note the typical chevron markings in the
FAC region and also the area of "excessive deposition" (box-like magnetite) about
2 in. (5 cm) from the FAC.
1-29

Introduction
Figure 1-13
Acid phosphate corrosion in an HRSG high pressure evaporator tube (1500 psi,
10.3 MPa). HRSG was operated on congruent phosphate treatment with additions
of low molar ratio (2) Na:PO4 chemicals.
Figure 1-14
Incipient corrosion fatigue cracks in HRSG economizer tubing after only about
4000 hours.
1-30

Introduction
1.11 HRSG CYCLE CHEMISTRY DIAGRAMS

As indicated in prior subsections, a plethora of HRSG designs and cycle configurations
exists, and additional approaches to waste heat utilization are in the planning and
development stage. A summary of the available options for drum-type and oncethrough HRSG systems which are covered in these guidelines is presented in Figure 115. Note that pressure ranges indicated for HP, IP and LP drums are meant only to be
representative of the majority of installations; some systems with pressures outside the
indicated ranges undoubtedly exist.
The existence of so many system designs makes it highly impractical (perhaps
impossible) to develop chemistry guidelines, diagrams and discussions which cover
each unique configuration.
To simplify ensuing presentations and discussions of the different chemistry treatment
approaches available in Sections 38, two cycle chemistry diagrams will be utilized.
Figure 1-16 presents a cycle including a combustion turbine and three-pressure drum
HRSG with reheater section. Figure 1-17 presents a cycle in which waste heat from the
combustion turbine is directed to a once-through HRSG with three pressures (LP, IP,
and HP) and a reheater section.
Ensuing discussions of chemistry treatments and monitoring requirements have been
developed in the context of the systems represented in Figures 1-16 and 1-17. Although
some comments are provided on configurations which differ from these figures (e.g.
reheat vs. nonreheat cycles), personnel responsible for chemistry should make the
necessary adjustments as part of the overall customization and optimization process
required in developing chemistry programs for individual HRSG units (Section 9). The
reader must remember that these two cycle diagrams are only used for illustrating the
chemistry parameters and the monitoring points.
Important examples of differences in actual system design with Figures 1-16 and 1-17
include but are by no means limited to the following:
Water from the LP circuit may be fed to IP and HP circuits.
Water from the IP circuit may be fed to the HP circuit.
Cascade blowdown may be practiced on multiple pressure drum HRSGs.
Attemperation water may be taken from the LP circuit or the feedwater system.
Inclusion of reheaters is becoming more popular but is not included in many

operating units.
1-31

Introduction
Single
pressure
drum
OTSG
Up to 50 bar
(725 psi)
Single pressure systems
HP
drum
LP
drum
70-124 bar
(1015-1800 psi)
20-40 bar
(290-580 psi)
Dual pressure drum systems
HP
drum
IP
drum
90-150 bar
(1305-2200 psi)
20-40 bar
(290-580 psi)
LP
drum
5-7 bar
(72-101 psi)
Triple pressure drum systems
OTSG
LP
drum
5-7 bar
(72-101 psi)
Combined drum/once-through systems
Figure 1-15
Options for HRSGs/OTSGs
1-32

Introduction
Deaerator
HP SH steam
IP SH steam
IP SH steam
LP SH steam
Chemical
feed
LP
drum
Flue gas
to stack
Chemical
feed
Chemical
feed
IP
drum
Reheater
HP
drum
HP
To process (if used)

To steam injection
for combustion turbine
(if used)
IP
LP
Steam turbine
Heat Recovery
Steam
Generator (HRSG)
Condenser
Flue gas
Preheater
Deaerator
pump
Low
pressure
(LP) section
LP
blowdown
Intermediate
pressure
(IP) section
IP
blowdown
High
pressure
(HP) section
HP
blowdown
Attemperation
feed
Feedwater
pump
Chemical
feed
Supplemental
firing (if used)
Air Fuel
Combustion
Electricity
turbine and
generator
Water
Steam injection
injection
from IP steam
NOx control systems (if used)
Bypass
Condensate
polisher
(if used)
Condensate
storage
Makeup
system
Condensate
pump
Figure 1-16
Combustion Turbine/Combined Cycle Unit Three Pressure Drum HRSG with Reheat. It should be noted that this
diagram does not represent exactly any operating unit. It is only illustrative for use in the chemistry cycle diagrams for
drum units in this guideline.
1-33

Introduction
Flue gas
to stack
HP steam
IP steam
LP steam
Reheater
LP
section
IP
section
HP

To steam injection
(if used)
IP
LP
Steam turbine
Heat Recovery
Steam
Generator (HRSG)
Condenser
Flue gas
High
pressure
(HP) section
Supplemental
firing (if used)
Air Fuel
Attemperation
feed
IP and HP
feed pump
Combustion
Electricity
turbine and
generator
Water
Steam injection
injection
from IP steam
Bypass
Condensate
polisher
Chemical
(if used)
feed
Condensate
storage
Makeup
system
Condensate pump
and LP section
feed pump
Figure 1-17
Combustion turbine/combined cycle unit with once-through HRSG and reheat. It should be noted that this diagram
does not represent exactly any operating unit. It is only illustrative for use in the chemistry cycle diagrams for oncethrough units in this guideline.
1-34

Introduction
Deaeration may be performed in the feedwater system or LP circuit.
Feedwater heaters/preheaters may or may not be present.
Condensers may be water cooled or air cooled.
In plants with air-cooled condensers, it should be noted that iron levels may be higher
than the limits provided in this guideline (see discussion on iron in Section 2.7).
Oxygen and carbon dioxide may also be elevated in these plants.
Condensate polishers may or may not be present.
Despite these differences, the monitoring points and chemistry parameters to be

considered are fairly similar. A standard set has been used throughout these
guidelines, recognizing that some operators will need to adapt them to their own
specific unique situation or design.
1.12 REFERENCES AND SOURCES

1. Steam, Its Generation and Use, 40th Edition, Babcock & WilcoxA McDermott
Company, Edited by S. C. Stultz and J. B. Kitto, Section 31, p. 31-2.
2. Materials Considerations For HRSGs in Gas Turbine Combined Cycle Plants, EPRI TR105013, 9000-24, Final Report, August 1996.
3. High Performance Steam Development, Final Report Phase III, 1500F Steam Plant For
Industrial Cogeneration Prototype Development Tests, T. Duffy and P. Schneider, Solar
Turbines Inc., San Diego, Calif. For US Department of Energy Under Contract DEAC02-81CD40812, SRG4-R-5527-101, January 1996.
4. Steam, Its Generation and Use, 40th Edition, Babcock & WilcoxA McDermott
Company, Edited by S. C. Stultz and J. B. Kitto, Section 6-21).
5. F. Gabrielli, H. Sandmann and R. Svoboda, Combined Cycle Power PlantsWater
Chemistry, Proceedings: Fourth International Conference on Fossil Plant Cycle
Chemistry, Eds. B. Dooley and R. Pate, EPRI TR-104502, January 1995, pp. 5-1 to 516.
6. R. B. Dooley, J. Mathews, R. Pate and J. Taylor, Optimum Chemistry for Allth
Ferrous Feedwater Systems: Why Use an Oxygen Scavenger?, 55 Annual
Meeting, International Water Conference, Pittsburgh, PA, October 1994.
7. Cycle Chemistry Guidelines for Fossil Plants: All Volatile Treatment, Electric Power
Research Institute, Palo Alto, CA, TR-105041, April 1996.
1-35

Introduction
8. D. Platt and D. A. Vinnicombe, Operating a Drum Boiler Without Hydrazine,

ESKOM/EPRI Cycle Chemistry Symposium, Johannesberg, South Africa, June 1994.
9. J. Schroeder, Private Communication, June 1997.
10. M. Macrae, Private Communication, July 1997.
11. T. Duffy, Private Communication, July 1997.
12. T. Duffy and P. Schneider, Final Report, Phase III, 1500F Steam Plant for
Industrial CogenerationPrototype Development Tests, U.S. Department of
Energy Contract DE-AC02-87CD40812, SR94-R-5527-101, January 1996.
13. R. Svoboda, E. Liebig, H. Sandmann and F. Gabrielli, Cycle Chemistry Features in
Advanced Combined Cycle Power Plants, Fifth International Conference on Cycle
Chemistry in Fossil Plants, EPRI TR-108459, December 1997.
14. D. G. Wiltsey, Private Communication, June 1997.
15. Condensate Polishing Guidelines, Electric Power Research Institute, Palo Alto, CA, TR104422, September 1996.
16. The ASME Handbook on Water Technology For Thermal Power Systems, Chapter 23,
EPRI Research Project No. RP-1958-1, The ASME, United Engineering Center, 345
East 47th Street, New York, NY 10017, 1989.
17. Guidelines For Chemical Cleaning of Fossil-Fueled Steam Generating Equipment, EPRI TR102401, Project 2712-06, Final Report, June 1993.
18. R. Krowech and L. Stanley, Avoid Damage from HRSG Cycling, Power,
March/April 1998, pp. 47-50.
19. R. B. Dooley and W. P. McNaughton, Boiler Tube Failures Theory and Practice, Vols. 1,
2, and 3, EPRI Book TR-105261, June 1996.
20. M. Rziha and R. Wulff, Cycle Chemistry in Combined Cycle UnitsThe Siemens
Experience, Power Station Chemistry Conference, Newcastle, Australia, March 1113, 1998.
21. T. McCloskey, B. Dooley and W. McNaughton, Turbine Steam Path Damage: Theory
and Practice, Vols. 1 and 2, EPRI Book TR-108943, 1999.
1-36
2
RATIONALE FOR HRSG CHEMICAL TREATMENTS,
SAMPLE POINTS, ACTION LEVELS AND TARGET
VALUES
2.1 INTRODUCTION
These guidelines are designed to assist utilities and operators in improving the
operating efficiency, and reducing the failures and losses in HRSG tubing and turbine
availability for combustion turbine/combined cycles attributable to cycle chemistry, by
accomplishing the following objectives:
selecting and optimizing the boiler water and feedwater treatments (Section 9),
minimizing corrodent concentrations,
minimizing the ingress of corrodents, and
reducing the generation and transport of corrosion products.
The rationale of the guidelines for achieving these objectives is based upon an
understanding of the effects of impurities on cycle component materials under stress
and heat transfer conditions and a knowledge of chemical transport from the sources of
the impurities throughout the water and steam cycle.
The following factors need to be considered to establish limits that will control the
environment at HRSG tubing surfaces to prevent deposition and corrosion:
relationships between the chemical compositions of major cycle streams (mechanical

and chemical transport);
relationships between the analyzed species (mostly ions) and actual molecular
species; and
2-1

Rationale for HRSG Chemical Treatments, Sample Points, Action Levels and Target Values
effects of heat transfer, boiling, condensation, volatility, chemical reactions,

ionization, and chemical thermodynamics and kinetics.
These guidelines include sample points, action levels and target values for the
following chemical treatment philosophies:
Phosphate Treatment Methodologies for drum-type HRSGs
Phosphate Treatment (PT)
Equilibrium Phosphate Treatment (EPT)
All-Volatile Treatment (AVT)
Drum Units
Once-Through Units
Caustic Treatment (CT) for drum-type HRSGs
Oxygenated Treatment (OT)
Once-Through Units
Drum Units
A brief summary of each of these treatment philosophies follows:
Phosphate (PT) and Equilibrium Phosphate (EPT) HRSG Boiler Water Control
The utilization of phosphate salts for internal conventional fossil plant boiler water
treatment is more than 70 years old. The initial purpose was to prevent the formation
of hard calcium scales on heat transfer surfaces(1,2). After the development of improved
feedwater purity, the practice was continued to prevent caustic embrittlement
(sodium hydroxide induced stress corrosion cracking). An approach to this problem
was developed by Whirl and Purcell(3,4) and was entitled Coordinated pH-Phosphate
Treatment (See Figure 2-1a). Boiler tube failures attributed to under-deposit caustic
attack continued(5) as well as hydrogen damage from concentrated acidic chlorides
under deposits. A further effort was made in a laboratory study to give more
assurance for the neutralization of under-deposit caustic concentrations (6). It was
postulated that the concentrated phase hiding out was richer in sodium hydroxide
than was expected on the basis of the sodium (Na+) to phosphate (PO43) of the three-toone ratio in Na3PO4. It was concluded that if caustic was to be avoided in localized
under-deposit locations that the pH of the boiler water should be maintained below
2-2

the level corresponding to a sodium phosphate solution having a ratio of Na+ to PO43 of
~2.6 (See Figure 2-1b). This was called congruent phosphate treatment.
However, a new boiler tube failure problem was recognized recently in the US with
congruent phosphate treatment in high pressure boiler units(7,8). Some of these tube
failures have been attributed to acidic phosphate under-deposit corrosive attack
while attempting to maintain the specified pH range when operating under congruent
phosphate control. Because of phosphate hideout and the characteristic increase in
bulk boiler water pH that is associated with it, excessive amounts of lower pH
phosphate solutions of di-sodium and mono-sodium phosphate have been injected by
chemists/operators to lower the boiler water pH.
A similar situation was identified in the former USSR during the 1960s (9) and also
studied in England in the 1960s and 1970s(10). In the USSR, serious acid phosphate
corrosion occurred when the boiler was dosed with either di-sodium phosphate or
sodium hexametaphosphate; this corrosion was also reproduced in a Russian
laboratory where the corrosion was monitored by hydrogen evolution. The use of trisodium phosphate alone, or together with a low level of sodium hydroxide, did not
produce any corrosion and has been the chemistry of choice for drum units in Russia
(and the former USSR) for over the last 20 years.
Acid phosphate corrosion has also occurred in HRSG tubing (see Section 1.10).
The CEA (Canadian Electrical Association) showed that under boiler water conditions
associated with a sodium/phosphate ratio of <3, reactions with magnetite (Fe3O4), both
in porous deposits and in the protective oxide film, can form an unrecoverable sodiumiron-phosphate compound (maricite). Additions of phosphate of ratios of <2.7 further
enhance the acidic phosphate reactions with magnetite.
To prevent operators from having to chase phosphate hideout and the associated
additions of mono- or di-sodium phosphate, the phosphate treatment (PT) in these
guidelines is now bounded by the sodium/phosphate of molar ratio 2.8 line and the trisodium phosphate plus 1 ppm NaOH line (Figure 2-2). Even with the higher levels of
phosphate in PT, an operator should determine the level of phosphate that an HRSG
boiler can maintain without hideout; the procedures described in Section 3 to
determine the equilibrium level can be used for PT also.
The limits established for equilibrium phosphate treatment (EPT) for higher pressure
conventional fossil boilers are also shown in Figure 2-2. The limits include the area
bounded by a pH of 9.0 and its horizontal intersection with the curve of molar ratio
Na:PO4 of 2.8 (lower limit) and by an upper limit bounded by the tri-sodium
phosphate + 1ppm NaOH curve up to about 2.5 ppm phosphate. For lower pressure
HRSGs, higher levels of phosphate can be utilized in the boiler, by following the
2-3

guidelines in Section 3. Sodium hydroxide values should be maintained at 1 ppm or

less in any case.
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 2-1
Historical Development of pH-Phosphate Control Ranges(3)
2-4

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
0.2
8.5
5
ppm PO4
Equivalent NaOH Concentration (ppm)
3.0
10
Figure 2-2
Schematic of Operating Ranges of Boiler Water on Equilibrium Phosphate
Treatment (PT)
Further information on these phosphate treatments may be found in Section 3 of these

guidelines and in the EPRI report Cycle Chemistry Guidelines for Fossil Plants: Phosphate
(11)
Treatment for Drum Units .
Drum Units on All-Volatile Treatment

Over 30% of the conventional fossil fired drum units around the world presently
operate with all-volatile treatment (AVT). The popularity of AVT is to a large extent
attributable to its simplicity and the fact that excellent cycle chemistry is possible when
proper controls and limits are initiated and maintained. The use of AVT, for example,
reduces the need for additional chemicals, such as phosphates, and thereby precludes
phosphate hideout, and minimizes boiler tube deposits and under deposit corrosion.
Recent experience(12) suggests that it may be possible to eliminate hydrazine in allferrous feedwater cycles.
The main disadvantage of AVT for conventional and HRSG boilers is that constant
vigilance is required to prevent ingress of contaminants, such as from condenser
leakage, improper chemical cleanings and from faulty demineralizer regenerations.
The boilers operating under AVT have little or no buffering capacity during such
2-5

occurrences. Therefore, immediate action is required to stabilize boiler chemistry, to

prevent deposition and/or corrosion as outlined in the subsequent sections.
Condensate polishing can play an important role in preventing contaminant ingress, as
well as in reducing startup times. This is why over 90% of all conventional fossil fired
units operating on AVT have condensate polishing. Polishers are especially beneficial
on those units having sea water cooling or high cycles of concentration in cooling tower
water for their cooling systems. In such cases, the contaminant ingress, even with tiny
condenser leaks, is sufficient to require immediate unit shutdown without polishers;
but with polishers, shutdown can usually be delayed or avoided by reducing load,
isolating the leaky condenser section and making repairs.
Cycles with Once-Through Units on All-Volatile Treatment (AVT)

The operating philosophy for once-through steam generating units recognizes that all
soluble feedwater contaminants have to dissolve in the superheated exiting steam and
be within the allowable inlet steam purity limits. The corrosion products transported to
the steam generator from the pre-boiler system have to be maintained at a
concentration level low enough to provide economical operating periods between
chemical cleans to remove these deposits before they cause equipment damage.
The feedwater treatment, therefore, has to be AVT (or oxygenated treatmentsee later)
and the choice of additive has to meet the requirement of not being thermally
decomposed at exiting superheated steam temperatures which may be in excess of
1000F (538C). The only volatile additive found to meet these requirements was
ammonium hydroxide.
To optimize control and transport of feedwater contaminants, and because of the
determination of the steam solubility of copper corrosion products, feedwater systems
should be constructed of iron-based materials. Full flow condensate polishing systems
utilizing either deep bed and/or powdered resin systems are utilized at the
condenser discharge at temperatures less than 140F (60C); at higher temperatures
there is a potential danger that the ion exchanger will be subject to thermal
degradation. Systems can also be designed with pre-coat or cartridge filters ahead of
the condensate polishers.
Feedwater systems having carbon steel heaters and piping are required to operate at a
pH of 9.29.6 (77F, 25C) to minimize flow-accelerated corrosion (FAC). Some
manufacturers suggest higher pH levels to address the FAC problem in HRSGs (see
Appendix A).
Further information on AVT can be found in Sections 4 and 5 of these guidelines and in
the EPRI report Cycle Chemistry Guidelines for Fossil Plants: All-Volatile Treatment(13).
2-6

Caustic Treatment (CT) of HRSG Drum Boilers

High concentrations of sodium phosphate and sodium hydroxide were used for
conditioning the boiler water of conventional low pressure plants in the 1950s.
However, when similar methods were used for conditioning the new generation of
high pressure plants in the 1960s, it resulted in frequent failures due to on-load
corrosion, in the form of caustic gouging with caustic treatment or hydrogen damage
due to acid chloride attack. The reasons for the corrosion were not always clear and
there was a great deal of confusion. The outcome was that the use of sodium
hydroxide was abandoned in the US in favor of all-volatile treatment (AVT) or
conditioning the boiler water with phosphate. CT did remain as the treatment of choice
in a number of countries(10).
On-load corrosion and the problems of chemical control, which occurred when
operating with Phosphate Treatment (PT), led to basic studies of corrosion and searches
for alternative methods of chemical conditioning in some countries. Control of the
ingress of anionic impurities and the use of low concentrations of sodium hydroxide
(caustic) was developed and is now being used successfully for conditioning more than
50,000 MWe of drum boiler plants worldwide. CT is presently being used and
evaluated is several HRSG facilities in Europe and other parts of the world.
Caustic treatment of HRSG boiler water significantly increases the amount of chloride
that can be tolerated without corrosion, compared with AVT and EPT. This is
important for dealing with condenser leaks, particularly when cooling is with brackish
or sea water. The use of sodium hydroxide has in the past reduced the need for
condensate polishing in conventional plants. CT can also be used instead of phosphate,
to avoid hideout and the complications this causes with chemical control, and the risk
of producing uncontrolled acidic or alkaline conditions, which lead to corrosion. It is
still important to limit chloride ingress with CT and to ensure that there is sufficient
sodium hydroxide present to prevent acid conditions. It is also important to limit the
amount of sodium hydroxide present, to prevent caustic gouging in the HRSG tubing
and excessive carryover into the steam, resulting in damage to the steam turbine.
Further information on CT can be found in Section 6 of these guidelines and in the EPRI
report Sodium Hydroxide for Conditioning the Boiler Water of Drum-Type Boilers(10).
Oxygenated TreatmentOnce-Through and Drum Units

The use of oxygenated treatment (OT) is not drastically different from the use of AllVolatile Treatment (AVT). A comparison of the main features of the two chemistries in
conventional fossil plants may be seen on Figure 2-3. Ammonia injection, as practiced
with AVT, continues although at lower pH values and thus lower ammonia
concentrations. OT requires the maintenance of high levels of cycle purity. Proper
2-7

condensate polishing operation, use of high purity makeup, and limited air in-leakage
continue to be important features in maintaining highly pure cycle fluids. The
management of the cycle and the rigid adherence to guidelines and action levels take
on added importance with OT.
The addition of an oxidizing medium improves the passivation, release, and transport
of iron in the condensate and feedwater system. In HRSG cycles, OT will also lead to
passivation of HRSG tubing operating up to about 280-300C. Two feed locations are
recommended for gaseous oxygen. The feed of oxygen at these locations has been used
successfully in many stations. The first feed location is downstream of the combined
condensate polisher effluent. The second is downstream of the deaerator. This second
feed location would not be required in cycles without deaerators, and may not be used
in cases where the deaerator vents are kept closed.
Ammonia addition downstream of the condensate polisher is traditional for both AVT
and OT control schemes. It is also consistent with the lowest level temperature for the
addition of oxygen to be effective.
All volatile treatment (AVT)
- Ferrous feedwater train
- Cation conductivity 0.2-0.4 S/cm
- pH 9.2 - 9.6
N2H4 (>3xO2)
NH3
Fe 10 ppb
O2 <5 ppb
Boiler
HP
Heaters
BFP
DA
LP
Heaters
CP
CEP
Condenser
Fe <2ppb
Oxygenated treatment (OT)
O2
- All ferrous feedwater train
- Cation conductivity <0.15 s/cm
- pH 8.0 - 8.5
O2 (>30 ppb)
NH3
Figure 2-3
Comparison of AVT (upper) vs. OT (lower) indicating major difference in the level
of feedwater corrosion products exiting from the feedwater system in
conventional fossil plants.
In conventional plants, the use of OT for drum units is very similar to that for oncethrough units. OT essentially treats the feedwater system by reducing flow-accelerated
corrosion. Because there are no basic differences between the feedwater systems of
once-through units and drum units, chemical injection locations are the same as for
once-through units. Thus treatment is similar and consists of oxygen injection
2-8

capability both downstream of the condensate polishing system and downstream of the
deaerator (if used). Ammonia injection, as practiced with AVT would continue,
downstream of the condensate polishers.
The major difference with drum OT, from a chemistry standpoint, is due to the
concentrating effect of the boiler drum. The boiling and recirculation of drum water
concentrates any impurities present and can, in the presence of oxygen, significantly
increase corrosion or under-deposit corrosion such as hydrogen damage in the boiler.
The oxygen in the feedwater will ultimately leave the drum with the saturated steam.
However, the oxygenated feedwater will first flow into the downcomers which raises
concerns for accelerated corrosion if contaminants are present. The oxygenated
feedwater will be diluted by the recirculation of deaerated boiler water, thus reducing
the oxygen concentration in the water in the downcomer. In order to be able to limit
oxygen concentrations in the downcomer it is necessary to know the ratio of oxygen at
the economizer inlet to the oxygen in the downcomer for all operating conditions. This
is explained further in Section 7.
As a result of the oxygen in the downcomer water, drum OT requires that high levels of
cycle purity be maintained. Proper condensate polishing operation, use of high purity
makeup, and limited air in-leakage will continue to be important features in
maintaining highly pure cycle fluids. The management of the cycle and the rigid
adherence to guidelines and reaction to action levels continue to be very important with
the drum unit OT.
Further information on OT can be found in Sections 7 and 8 of these guidelines and in
the EPRI report Cycle Chemistry Guidelines for Fossil Plants: Oxygenated Treatment(14).
2.2 GUIDELINE DERIVATION PHILOSOPHY

The relationships between thermodynamics and corrosion throughout the cycle are
illustrated in Figure 2-4, which is a Mollier diagram showing the steam expansion line
for a typical fossil plant. Regions where impurities will concentrate and promote
corrosion are illustrated in this diagram. This chart includes the boundaries of regions
of thermodynamic stability for liquid and solid sodium chloride solutions. It
demonstrates that sodium chloride deposition and associated corrosion are likely to
occur across a very narrow region in the last stages of the low-pressure turbine. The
location of the region where contaminant deposition will occur is related to the actual
conditions at component surfaces rather than the theoretical average flow path
conditions. Heat transfer, surface cleanliness, crevices, and surface flow stagnation
conditions determine the actual surface temperatures and pressures.
These guidelines differentiate between reheat and non-reheat cycle designs and
provide a discussion in each chemistry section for drum units on the differences
2-9

between reheat and non-reheat parameter values. The guidelines also provide target
values and action levels for all key cycle contaminants in drum HRSGs as a continuum
over a broad range of operating pressures. Cycle contaminant values for the minimum
HRSG pressure of 600 psi (4.1 MPa) depicted on these curves should be used for all
HRSGs operating at 600 psi (4.1 MPa) and below. This is based on the rationale that:
there is considerable uncertainty in values projected from the ray diagram (Figure
2-6) at pressures lower than 600 psi (4.1 MPa),
the contaminant values at 600 psi will provide conservatism for HRSGs operating at
600 psi (4.1 MPa) and below, and
for PT and EPT units, there is no need to add additional phosphate above those
levels designated at the 600 psi (4.1 MPa) pressure.
These guidelines also summarize all sample points, monitoring and control parameters,
target values, and action levels on a single-cycle diagram for reheat cycles; and feature
a consistent, methodical rationale that relates all sample points, target values, and
action levels for each parameter to the component(s) most affected by that parameter.
The guidelines include target values and action levels for significant contaminants at
critical sample points. In addition to the aforementioned considerations, the criteria for
establishing the target values include:
the optimal steam and water chemistry for protecting cycle components (HRSG,
turbine, and feedwater components) from deposition and corrosion, based on a
review of numerous research projects performed to date;
limits of detection based on the capability of currently available on-line analyzers

and grab sample analysis methods;
achievability with current operating HRSG units and water treatment practices; and
practicality, based on overall economic benefits without imposing undue burdens

on operations.
2-10

LP inlet
Caustic SC
cracking
Pitting, SCC, CF
Enthalpy
Salt zone
Cor
Some disc surfaces

~30% NaCl solution
rosi
on-e
rosi
Wa
te
on
Satu
ratio
n line
Wilson zone
4% moisture
6%
8%
10%
12%
r dr
opl
et
Ero
sion
Entropy
Figure 2-4
Mollier Diagram for a Fossil Cycle. Illustrates Where Impurities Will Concentrate
and Promote Corrosion
A review of the sensitivities of cycle components to water and steam purity determined
that limiting the concentrations of ionic contaminants throughout the cycle to levels
consistent with the levels in the steam tolerable by the steam turbine will adequately
protect the HRSG boiler, the combustion turbine (if using steam or water injection for
NOx control) and other cycle components. Thus, the rationale for cycle water and steam
chemistry control requires that overall cycle chemistry must satisfy the turbine
requirements for steam purity.
Starting with turbine steam composition, and considering mechanical and vaporous
carryover, the allowable impurity concentrations in HRSG boiler water can be
determined. Both mechanical (Figure 2-5) and vaporous (Figure 2-6) carryover are
pressure dependent and, therefore, the target values for HRSG boiler water ionic
contaminants are also pressure dependent. Smooth, continuous relationships of HRSG
boiler water target values as a function of pressure have been developed for drum
HRSGs. This approach, which was originally developed by EPRI in the Interim
Consensus Guidelines for pulverized coal-, oil-, and gas-fired units (15), will allow units
having the capability of changing load via sliding pressure operation to benefit from
relaxed HRSG boilerwater chemistry limits when reducing load by reducing pressure.
Target values for feedwater chemistry in drum HRSGs were made comparable to those
for steam chemistry to minimize the cost of blowdown and also maximize the
2-11

availability of blowdown as a corrective action. This rationale gives operators the

maximum amount of response time to take corrective action when upsets occur and is
practical because of the significant cost of the heat lost in blowdown. Feedwater
chemistry also reflects the need to control feedwater corrosion by optimizing the
content of dissolved oxygen and reducing agent (oxygen scavenger), as well as the
oxidizing-reducing potential (ORP) and pH.
Use of ORP monitoring has proven invaluable in efforts to optimize feedwater
treatment and minimize corrosion product transport. Changes in ORP were used to
evaluate elimination of scavenger feed to units with all-ferrous feedwater systems.
Increases in ORP as scavenger feed was reduced or eliminated were accompanied by
reduction in iron transport(12).
All the target values can be recalculated and made to fit individual unit characteristics
where the steam purity limits can be relaxed and where the mechanical carryover has
been measured and validated and differs from the values in Figure 2-5.
The higher tolerance of non-reheat turbines to impurities in steam has been reflected in
the establishment of a separate set of guidelines for these units, which are discussed in
each chemistry section.
2-12

4.8
6.2
600 700
900
7.6
9.0
Drum Pressure (MPa)

10.3 11.7 13.1 14.5
15.8
17.2
18.6 19.6
0.3
Mechanical carryover (%)
0.2
0.1
0.09
0.08
0.07
1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
Drum Pressure (psig)
Figure 2-5
Drum Boiler Mechanical Carryover. Monitoring should be conducted on each
HRSG drum to determine the mechanical carryover.
Source: Unpublished. Reviewed with boiler manufacturers and confirmed
through private conversations during preparation of EPRIs Interim Consensus
Guidelines(15) for conventional fossil plants.
2-13

200
400
600
1000
1200
1600
2000
2200
2800
2600
3000
3200
Drum Pressure (psia)
10-0
Fe3O4
Al2O3
10-2
B2O3
NH
4 Cl
, (N
NiO
4)
2
SO
CuO
10-3
SiO2
10-4
CaSO4
Cu2O
MgO
BaO
CaCl2
10-5
Na
LiCl
Cl
Concentration In Vapor/Concentration in Liquid
10-1
PO
Na 3
Na
10-6
O4
2S
NaOH
10-7
220
200
160
120
80
60 40 30
Drum Pressure (atm)
6
10
20
60
Density of Liquid/Density of Steam
Figure 2-6
Distribution Ratios for Common Boiler Water Contaminants
2-14
20
100
10

2.3 RATIONALE FOR SAMPLE POINTS

Recommended sample points were developed based on the optimal cycle chemistry
requirements, and the rationale for each sample point is discussed in this section. The
parameters to be monitored fit into two categories, as shown on the cycle chemistry
diagrams: a) those parameters which all HRSG plants should have for optimum
chemistry control (core parameters) and b) those parameters which are regarded as
diagnostic for supplementary monitoring, troubleshooting or commissioning.
A listing of cycle chemistry monitoring parameters and monitoring points is provided
in Table 2-1. The core parameters are considered the minimum level of surveillance
that is needed for all HRSG units. In general, use of on-line analyzers for continuous
analysis of chemistry is preferred. However, some provision is made for use of shared
instrumentation (dissolved oxygen) and laboratory analysis of grab samples (silica and
phosphate). The monitoring approaches suggested recognize limitations on manpower
at many HRSG plants and the fact that some analyzers require significant maintenance
attention to perform reliably. Further, it is suggested in each of the Chemistry Sections
(3-8) that the primary control of combined cycle/HRSG chemistry is through
conductivity (either specific or cation as appropriate).
The listing of Suggested Additional Monitoring or Diagnostic Parameters indicated
in Table 2-1 represents those chemistry surveillance measures most likely to be
included in customized chemistry programs for specific plants and units. Still other
chemistry parameters which may be monitored under special circumstances include the
following:
Ammonia in Feedwaterto improve control of feedwater treatment or to optimize

the treatment approach
Copper in Feedwaterto evaluate feedwater treatment in HRSG units with copper

alloys (HRSG/combined cycles usually have copper-free feedwater systems, but
may have copper alloys in the condenser.)
Sulfate and Chloride in Treated Makeup, Condensate, Condensate Polisher Effluent

and Steamto evaluate cycle contamination and transport involving these species
Sodium in Treated Makeupto evaluate demineralizer performance
Total Organic Carbon (TOC) in Feedwater, Boilerwater and Steamto assess the
effect of organic based proprietary treatments and makeup contamination on cycle
chemistry
Analyzers suitable for low level analysis of anions and organics are not expected to be
included in an HRSG plant laboratory. Such testing would need to be contracted to an
2-15

outside laboratory with an ion chromatograph (for anions) and a TOC analyzer (for
organics).
As discussed further in Section 2.7, target values have been established for sodium,
chloride, sulfate and organics in steam. Limits for these parameters were set to
minimize the risk of deposition and corrosion in turbines. In drum units, it is
important to avoid levels of carryover which will exceed the target values. Using
available information on mechanical and volatile carryover, contaminant control curves
were developed which relate steam carryover to boiler drum pressure and
concentration of the contaminant of interest. Example control curves for PT can be seen
in Figure 3-2 (for sodium), 3-3 (for chloride) and 3-4 (for sulfate).
In general, it is not practical or necessary to routinely monitor all species of interest in
the boiler water. Effective control is usually attainable through monitoring of specific
and cation conductivities in boiler water and steam. Control curves are now available
which indicate maximum permissible boiler water specific and cation conductivity
values as a function of drum pressure. Further details on the use of these control
curves is provided in Sections 3-8 which discuss the available chemistry treatment
approaches.
2-16

Table 2-1
HRSG Cycle Chemistry Monitoring Parameters
Core Monitoring Parameters (Minimum Surveillance for Most Units)
Parameter/Monitoring Approach
Monitoring Points
Cation Conductivity
Condensate Pump Discharge
Continuous by On-Line Analyzer
Condensate Polisher Effluent
Feedwater (or Economizer Inlet)
Blowdown or Downcomer
Saturated Steam, and Main or Hot Reheat Steam
Specific Conductivity
Treated Makeup
Blowdown or Downcomer (PT, EPT and CT)
pH
Blowdown or Downcomer (Drum Units)
Dissolved Oxygen
Feedwater (or Economizer Inlet)
Downcomer (Drum unit on OT)
(May Be Shared)
Sodium
HP Main or Hot Reheat Steam
Blowdown or Downcomer (PT and EPT)
Phosphate
Grab Sample Analysis Each Shift
(Or Continuous by On-Line Analyzer)
Treated Makeup
Silica
Suggested Additional Monitoring; Troubleshooting or Diagnostic Parameters (see Sections 3-8 for
guidance)
Parameter/Monitoring Approach
Monitoring Points
Feedwater (Economizer Inlet)
pH
Sodium
Condensate Polisher Outlet
Blowdown or Downcomer (PT, EPT and CT)
(May Be Shared)
Saturated Steam
Silica
Blowdown or Downcomer
Grab Sample Analysis Daily
Saturated Steam
ChlorideGrab Sample Analysis Daily
Blowdown or Downcomer (EPT, CT, AVT and OT)
Blowdown or Downcomer (CT)
Sodium Hydroxide
Grab Sample Analysis Daily
(Or Derived from Conductivity Data)
Hydrazine (when used)
Iron (and copper if copper alloys
present)
Grab Sample Analysis Weekly
ORP
Continuous by On-Line Analyzer (when used)
Total Organic Carbon
Treated Makeup
Grab Sample Analysis Weekly
Air Inleakage
Condenser Air Removal System
Check Air Removal Rate Daily
2-17

Reheat Steam and Superheated Steam

Factors affecting steam chemistry, other than the mechanical and vaporous carryover
from the HRSG boiler, include the following:
contamination by attemperation water to the superheater and reheater, and
precipitation of impurities as deposits in the superheater, reheater, and in the steam

turbine (mostly in the low-pressure turbine).
Monitoring of key contaminants at this sample point indicates the actual impurity
levels in the steam and indicates whether the turbine blades are protected against
deposition and/or corrosion. This monitoring also verifies compliance with the turbine
manufacturers guarantee condition.
Should this sample point not be available, the steam chemistry may be calculated from
the chemistries of the saturated steam and feedwater, accounting for impurity ingress
with the superheater and reheater attemperating water (feedwater).
Steam sampling requires special techniques, which are described in the EPRI report
(16)
Guideline Manual on Instrumentation and Control for Fossil Plant Cycle Chemistry .
Saturated Steam (Drum HRSGs Only)

Monitoring of this sample point provides verification of compliance with the HRSG
manufacturers performance guarantee for steam purity, which may apply only to the
saturated steam. The sample source may be from one steam offtake or all steam offtake
tubes from the drum as long as a representative sample is taken. This sample point
also serves as a diagnostic tool to monitor the mechanical entrainment and vaporous
carryover of impurities into the steam turbine.
The saturated steam chemistry data can also be related to the performance of the steam
drum moisture separator by calculating the vaporous carryover from the HRSG boiler
water chemistry data and estimating the amount of impurities carried over in steam as
a result of mechanical entrainment. Excessive mechanical carryover may indicate poor
moisture separator performance and has the greatest impact upon steam chemistry at
boiler drum operating pressures below 2000 psi (13.8 MPa), where mechanical
carryover is the major component of the total carryover.
HRSG Boiler Water

This sample point monitors drum boiler water chemistry to minimize deposition and
corrosion in the HRSG tubes. This sample point allows control of HRSG boiler water
2-18

chemistry through blowdown and chemical feed and is a primary control point for
steam purity. Blowdown or downcomer HRSG boiler drum samples can be used for
water analysis. With some designs, the blowdown may not provide a representative
water sample, and the downcomer sample should be used. The downcomer samples
should also be used for cycling units and layup chemistry control.
Samples from the downcomer will be diluted with the feedwater, and this will reflect a
lower concentration of the various chemical species when compared to blowdown
samples. This effect may be considerable, depending on design. Therefore, limits
derived from downcomer samples must reflect this dilution effect when compared to
limits given in these guidelines, which are derived for blowdown samples
Economizer Inlet(s) and Attemperation Water

This sample point allows the direct measurement of the total contaminant ingress to the
HRSG and to the steam via the attemperation water and it also permits the
determination of whether the feedwater meets the feedwater chemistry limitations
required by the HRSG manufacturers. This sample point also monitors feedwater
corrosion product transport and serves as a secondary control point for ammonia feed.
However, it does not permit the evaluation of flow-accelerated corrosion (FAC) in the
economizer header or HRSG tubes.
Deaerator Inlet (If Applicable)

This sample point can be used as the control point for hydrazine feed (if hydrazine is
being used and added prior to the deaerator).
Deaerator Outlet (If Applicable)

This sample point permits an evaluation of how the deaerator performs in removing
dissolved oxygen from the feedwater, especially during periods when the condensate
oxygen level is excessive (usually during startup and periods of high makeup with
air-saturated water).
Condensate Polisher Effluent (if Applicable)

This sample point is required to determine the effectiveness of the condensate polishers
and to determine their need for regeneration. This sample point also permits the
evaluation of resin particle throw from the condensate polishers.
2-19


This sample point monitors the following:
magnitude of contaminants introduced by condenser leakage, and
amount of dissolved oxygen.
For plants without condensate polishers, this point monitors the feedwater chemistry.
Condenser Leak Detection Trays and/or Hotwell Zones (If Applicable)

This sample point may allow condenser tube leaks to be detected earlier than by the
sample point located at the condensate pump discharge, thus aiding in a timely
determination of corrective action. Monitoring at these leak detection tray sample
points also allows determination of the tube sheet where the leak occurs. Quick
detection and repair of leaks minimizes the ingress of impurities into the heat cycle.
Each condenser hotwell section may also be monitored.
Makeup Treatment System Effluent

This sample point monitors the performance of the makeup treating system. The
makeup water purity is dictated by the design of the makeup water treatment
equipment and also depends on the makeup rate. Target values have been
recommended for the makeup treatment system based on current state-of-the art
equipment capabilities. These guidelines should be used as a performance guarantee
for any new makeup treatment systems. The target values should be modified for
existing makeup treatment systems to reflect the capabilities of the equipment.
Condensate Storage Tank Effluent

Monitoring the effluent from the condensate storage tanks indicates the quality of the
available makeup to the condenser. Also, certain water-quality conditions in
aluminum condensate storage tanks can lead to aluminum corrosion, resulting in the
deposition of corrosion products that are difficult to remove.
Air Removal System Exhaust

Condensate oxygen as well as carbon dioxide levels are a direct function of air inleakage. Air in-leakage in excess of that removed by the air removal system design will
result in increased oxygen and carbon dioxide levels, causing a probable increase in
2-20

corrosion product generation. Minimization of air inleakage will also prevent corrosion
of the condenser shell.
2.4 TROUBLESHOOTING, COMMISSIONING AND CORE PARAMETERS

In subsequent cycle diagrams, (Sections 38) which depict chemistry guidelines
throughout the heat cycle, a distinction is made between those sample points used for
routine chemistry monitoring and control, and those utilized as supplements for
troubleshooting or plant commissioning. The core parameters are indicated by * in the
cycle diagrams. It is suggested that an operator develops a specific cycle chemistry
diagram for the unit which only contains the core parameters, and that this diagram
may be more useful for posting in the control room and chemistry laboratory.
Water chemistry commissioning should be a part of the total commissioning effort
during which a new unit or a retrofitted unit is transferred from the supplier to the
operator. The main objectives of the commissioning are:
to prevent equipment damage due to malfunction of water chemistry related

equipment,
to determine the chemical transport characteristics of the cycle and final selection of
water treatment, water and steam chemistry limits,
to assess major sources of impurities and corrosion,
to quantify mechanical carryover.
This is the primary focus of the monitoring campaigns discussed in Section 9 which are
designed to select the optimum boiler water and feedwater treatments. There have
been too many units where commissioning has not been performed at all or has been
performed insufficiently, resulting in major equipment damage within weeks or
months of the initial operation. Typical problems that can be avoided by proper
commissioning include:
destruction of the magnetite on HRSG boiler tube surfaces and flow-accelerated

corrosion (FAC),
severe hideout of water treatment chemicals, such as sodium phosphate, resulting in

deposits and corrosion,
dryout in HRSG tubing which may lead to overheating or underdeposit corrosion

such as caustic gouging, hydrogen damage or acid phosphate corrosion,
2-21

high carryover leading to superheater, reheater, and turbine deposits and

superheater and reheater overheating failures, and
dirt left in the boiler or elsewhere in the system resulting in buildup of deposits or
foreign object damage.
The water chemistry-related systems and functions that should be tested during
commissioning include:
choice of boiler water and feedwater treatments (see Section 9),
chemical oxygen scavenging (if used) (see Section 9),
feedwater corrosion product generation and transport (determination of the points

where the corrosion occurs) (see Section 9),
boiler carryoverdrum boilers (see Section 9),
chemical addition equipment,
sampling and analytical equipment,
deaeration (condenser, deaerator),
purity of returned condensate (see Section 9),
blowdown and cycles of concentration (see Section 9),
makeup system and associated regeneration equipment,
pretreatment system,
condensate polishers (if used) and associated regeneration equipment,
condensate and feedwater storage systems, and
cleanliness and passivation effectiveness after preoperational chemical cleaning of

cycle components.
The importance of comprehensive monitoring/commissioning for all types of units and

treatments cannot be overemphasized.
2-22

2.5 RATIONALE FOR ACTION LEVELS

Action levels for control parameters at critical sample points were developed to provide
guidance on the relative need for corrective action in the event of cycle chemistry
excursions. These action levels are based on current, state-of-the-art knowledge and
will be revised based on a periodic review of experience. Four action levels were
established based on the following criteria:
Normal. Values are consistent with long-term system reliability. A safety margin
has been provided to avoid concentration of contaminants at surfaces.
Action Level 1. There is a potential for the accumulation of contaminants and

corrosion. Return values to normal levels within 1 week.
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 ShutdownHRSG Drum Units. There is clear evidence of rapid

HRSG tube damage by low boiler water pH. Immediate shutdown of the unit is
required to avoid such damage.
If the problem is not corrected within the time allotted to each action level, the next
higher action level takes effect. In drum units having the capability of sliding pressure
operation, one way to return from an action level condition is to reduce boiler pressure.
The target values for Action Levels 1, 2, and 3 were established to allow and provide
guidance during transient or abnormal operating conditions. The following criteria
were used for most of the parameters:
Action Level 1 Value: 2 [Normal Target Value]
Action Level 2 Value: 2 [Action Level 1 Value]
Action Level 3 Value: > [Action Level 2 Value]
Immediate Shutdown: HRSG boiler water pH indicates a serious acidic

contamination. (Drum Units)
It should be noted that a factor of less than 2x is used for CT (Section 6) to allow a
practical normal operational band (or limits) to be achieved within reasonable action
level safety limits.
2-23

Operation at the lowest achievable impurity levels, with the shortest and least frequent
excursions, is the most desirable mode of operation. The probability of corrosion
damage and deposit formation grows significantly with increasing impurity
concentration, and the damage is proportional to the exposure time. When corrosive
impurities concentrate on metal surfaces, the breakdown of passivity (damage to the
protective oxide layer) occurs within a few minutes to several hours.
Another aspect of corrosion initiation (see Section 3) is the relatively common practice
of overfeeding phosphates to the boiler water during periods of hideout to achieve
some pre-established value of bulk water phosphate concentration and/or pH. Such
practices, in association with under-deposit conditions, may lead to acid phosphate
corrosion and tube damage(7,8), especially if congruent phosphate treatment (CPT) is
being employed.
During excursions, when the impurity concentration increases sharply, the
accumulation of impurities in the cycle (turbine, HRSG, and superheater deposits)
occurs quickly, but the subsequent cleanup or return to good chemistry may take
weeks. Therefore, yearly time accumulations were also established as a guide.
Another useful approach to damage accumulation control is to set an annual goal for all
key parameters of (contaminant concentration) (days). Basically, this approach
involves setting a limit on the absolute amount of contaminant transport to a
component per year. Contaminant concentrations are then monitored for fixed lengths
of time, multiplied by the respective sampling periods, and totaled over the year. The
yearly concentration-days calculated in this way can then be compared with the set
limit. This approach has been used to rate unit chemistry, compare performance of
multiple units, and serve as an input for assessing the need for boiler chemical
cleaning.
2.6 RATIONALE FOR TARGET VALUES

Normal target values for monitoring and control parameters were developed. The
rationale for establishing these target values is discussed in this section for steam and
HRSG boiler water.
Requirements for sample system modifications and/or additional instrumentation and
manpower may be determined and justified through a cost-benefit analysis. EPRIs
Cycle Chemistry Improvement Program(18) illustrates the methodology to perform these
analyses for conventional fossil plants.
2-24

Steam
The target values for steam were derived based on turbine steam purity considerations
and the solubility of major impurities in superheated steam. Meeting these target
values will ensure that chemistries throughout the remainder of the cycle are
maintained to adequately protect the HRSG boiler, combustion turbine (if steam or
water is used for NOx control) and other cycle components. The solubilities of various
contaminants in superheated steam depend on the temperature and pressure of steam,
which vary at different points in the cycle for different designs and modes of operation.
As the pressure and temperature of the steam are reduced in the turbine, the vapor
solubility may be exceeded, resulting in the deposition of salts (acids and alkalis) in the
turbine that can lead to a reduction of efficiency and turbine corrosion.
The point (pressure and solubility) at which the steam expansion line crosses the
saturation line is the lowest in high pressure reheat units at low load. In the Mollier
diagram shown in Figure 2-4, the LP steam expansion line will shift to the right at low
load and constant HRSG boiler pressure, with higher superheat, lower impurity
solubility and limits. For these units, the steam purity target values and action levels
are the lowest. The turbine steam expansion line will cross the saturation line at higher
pressures and solubilities in lower pressure non-reheat units. Therefore, the steam
purity target values and action levels for these units may be relaxed (twice the values
for the units with reheat). For each case, a range of turbine designs and operation
modes was reviewed, and target values that were reasonable for the entire range were
selected. It should be noted that a differentiation between reheat and non-reheat is
made for target values for drum units on AVT, PT and EPT, but not for once-through
units on AVT and OT, or drum boilers on OT and CT.
HRSG Boiler Water (Drum Units)

Impurities in the HRSG boiler water can be carried over with steam through
mechanical and vaporous carryover. Thus, the allowable concentrations of impurities
in HRSG water depend on the desired steam chemistry. However, meeting target
values for steam does not negate the possibility of tube damage, for example by
impurities from condenser leaks or improper control of feedwater or HRSG water
chemistry. The allowable impurity concentrations in HRSG water are also affected by
the solubility of impurities in water, since precipitation will occur if the water
concentration exceeds the solubility. Therefore, HRSG water limits must be set to meet
steam purity requirements, but also to avoid conditions that may cause HRSG tube
corrosion or deposition.
Mechanical Carryover. Mechanical carryover is the entrainment of water droplets in
steam exiting the boiler. A plot of mechanical carryover, used in developing the target
values, is presented as a function of pressure in Figure 2-5. A safety factor of 2 is
2-25

included in Figure 2-5 to provide a conservative estimate of the amount of mechanical

carryover. The actual mechanical carryover rates must be measured (Section 9) for each
drum in a given plant and compared with that determined during commissioning.
These values should be checked against the values on Figure 2-5 to determine whether
the HRSG boiler water target values should be fine-tuned for that specific unit.
Vaporous Carryover. Molecular impurities in boiler water can evaporate with steam
(vaporous carryover). The degree of vaporous carryover is expressed as a distribution

ratio, which is the ratio of concentration in steam to that in water. The distribution
ratio is a function of:
boiler drum pressure (Figure 2-6),
HRSG boiler water dissolved solids concentrations, and
HRSG boiler water pH for some impurities such as silica and sodium.
The ray diagram (Figure 2-6) provides a rough estimate for determining vaporous
carryover. However, recent work sponsored by EPRI at the Oak Ridge National
Laboratory (ORNL) is expected to produce data that is more accurate based upon the
use of improved experimental and analytical techniques.
Total Carryover. The allowable impurity concentrations in HRSG boiler water are
calculated from those of the steam and the amounts of mechanical and vaporous
carryover.
The following example is provided to clarify this discussion:
Carryover is defined as the ratio of concentration of a particular chemical specie
in the saturated steam exiting the HRSG boiler drum to the concentration in the
boiler water (usually measured in the blowdown). Total carryover is defined as
T=M+V
(eq. 2-1)
where M is mechanical carryover (with steam moisture) and V is the vaporous

carryover.
Total carryover is usually measured by analysis of sodium:
T=
2-26
Na in saturated steam
Na in blowdown
(eq. 2-2)

Mechanical carryover is a measure of the separation efficiency of the boiler. It

can be calculated as
M = T V*
(eq. 2-3)
where V* is a vaporous carryover of the prevalent sodium salt identified in a

particular HRSG boiler at the boiler operating pressure. In phosphate treated
(PT) boilers, the tri-sodium phosphate line in Figure 2-6 can be used. For units
operating on EPT, AVT or OT the NaCl or NaOH lines from the same figure can
be used (see Rationale for Target Values of Individual Parameters described
later in Section 2.7).
Volatile carryover of chemical species associated with unknown molecules, Vx,
is then calculated as
Vx = Tx - M
where
and
Tx =
(eq. 2-4)
x in saturated steam
x in blowdown
M is from eq. 2-3
The following equation can be derived from a mass balance around the boiler and can
be used to calculate the HRSG boiler water concentrations from the allowable steam
concentrations, distribution ratios, and mechanical carryover rate:
CB
CS
M + k d (1 M)
(eq. 2-5)
where
CB = HRSG boiler water target value (ppb)
CS = main steam or reheat steam target value (ppb)
M = fractional mechanical carryover
kd = fractional distribution ratio
This equation should also be used to modify the target values for HRSG boiler water
chemistry recommended in these guidelines once the specific plants mechanical
carryover rates have been collected during commissioning and/or during a monitoring
campaign and found to be substantially different from those used (Figure 2-5) as a basis
for the guidelines. The equation does not include the effects of attemperation water,
2-27

which will be negligible when the attemperation water chemistry is maintained at a

value equal to or better than the superheat or reheat steam chemistry as recommended
in the guidelines.
Illustration A. The following example illustrates the procedure for calculating the
HRSG boiler water target values for a phosphate treated boiler.
Example: Calculate the HRSG boiler water sulfate target values and action levels
for a plant, using mechanical carryover rate data from Figure 2-5. This plant has
a 2500-psia (17.2 MPa) drum HRSG with reheat operated on PT.
Solution: Calculate the target value and action levels for operation at full load,
2500 psia (17.2 MPa), at which the mechanical carryover from Figure 2-5 is
0.00185.
1.
Target value of sulfate in steam is 3 ppb (Section 3).
2.
Obtain distribution ratio of sodium sulfate at 2500 psia (17.2 MPa) from
Figure 2-6: 2.3 106.
3.
Calculate target value of sulfate in HRSG boiler water using eq. 2-5:
CB =
3 ppb
0.00185 + 2.3 10 6 (1 0.00185)
= 1.6 103 ppb

= 1.6 ppm at normal operating conditions
Action Level 2 = 2 1.6 = 3.2 ppm
4.
Target values are as follows:

Normal: 1.6 ppm
Action Level 1:
Action Level 2:
Action Level 3:
1.6
> 1.6
3.2
> 3.2
6.4
> 6.4
Illustration B. The following example illustrates the procedure for calculating the
HRSG boiler water target values for an AVT or OT treated drum boiler.
2-28

Example: Calculate the HRSG boiler water sulfate target values and action levels
for a plant, using mechanical carryover rate data from Figure 2-5. This plant has
a 2500-psia (17.2 MPa) drum boiler with reheat operated on AVT.
Solution: Calculate the target value and action levels for operation at full load,
2500 psia (17.2 MPa), at which the mechanical carryover from Figure 2-5 is
0.00185.
1.
Target value of sulfate in steam is 3 ppb (Section 4).
2.
Obtain distribution ratio of ammonium sulfate at 2500 psia (17.2 MPa)

from Figure 2-6: 1.2 101 (0.12).
3.
Calculate target value of sulfate in boiler water using eq. 2-5:

CB =
3 ppb
0.00185 + 012
. (1 0.00185)
= 25 ppb
= 0.025 ppm at normal operating conditions
4.
Target values are as follows:

Normal:
Action Level 1:
Action Level 2:
Action Level 3:
0.025
> 0.025
0.05
> 0.05
0.10
> 0.10
2.7 RATIONALE FOR TARGET VALUES OF INDIVIDUAL PARAMETERS

Based on the general rationale discussed earlier, target values were developed for each
parameter at each sample point. Specific rationales for these target values are discussed
below.
In the following discussion, recognition is given to the fact that equilibrium phosphate
treatment (EPT) provides less buffering capacity in the boiler water than does
phosphate treatment (PT). Therefore, to provide conservatism in these guidelines,
2-29

HRSG boilers on EPT are assumed to operate as if they were on all-volatile treatment
(AVT). Boilers on OT are also assumed to operate as if they were on AVT. This
assumption affects the calculations relative to vaporous carryover for sodium, chloride
and sulfate (pressure vs. concentration curves); and, also affects the establishment of
target values for sodium in superheat and reheat steam.
Cation Conductivity
Cation conductivity serves as an excellent diagnostic tool as the cations are removed via
cation exchange and the H+ ion has a higher equivalent conductance than all other
cations. Condensate polishers further reduce ionic impurities in the condensate and
makeup water from their effluent values. Thus, target values of cation conductivity in
the condensate are more relaxed for units with polishers than for those units without
polishers. (Cation conductivity measurements do not reflect concentration of
hydroxides, such as sodium hydroxide, as they are converted to pure water.)
In high-pressure units where mixtures of amines are used for feedwater treatment,
decomposition products of amines may increase the cation conductivity.
Cation Conductivity Target Values in Condensate, Feedwater and Steam, and at
Condensate Polisher Effluent. The cation conductivity target values at these sample
points reflect the sum of cation conductivities contributed by individual anions and
some carbon dioxide that may exist from air in-leakage.
(25)
Cation Conductivity in HRSG Boiler Water. The measurement of cation conductivity
in the blowdown or downcomer of units on PT, EPT, CT, AVT or OT provides an

indirect yet reliable on-line indication of the level of contamination entering the heat
cycle and concentrating by recirculation in the HRSG drum boiler water. For this
reason, operators can rely on this measurement to initiate control measures to mitigate
the undesirable effects associated with increasing levels of contamination.
It should be kept in mind that samples from the downcomers will be diluted by
feedwater. Care should be taken to ensure optimum sample flow rate and temperature
(26)
control .
The curves for cation conductivity vs. pressure, which are presented in Section 4 for
drum units on AVT, consider the boiler water chloride and sulfate limits as a function
of pressure together with a number of other contributors such as organic acids,
carbonates, etc. The curve has been an inherent requirement of drum units operating
on AVT, which are suitable for conversion to oxygenated treatment(14). A similar
approach is taken for CT (Section 6) and for drum units on OT (Section 7).
2-30

As with other parameters, it is very important to customize these cation conductivity

limits for each HRSG drum boiler. This is included in the road maps to optimize each
chemistry treatment for each HRSG drum unit. If a boiler cannot meet these
requirements then a series of tests/analyses should be undertaken to determine the
cause of the excessive level.
Cation Conductivity Target Value in Steam. Continuous measurement of cation
conductivity at this location will provide a reliable indication of the presence of

harmful salts and acids that are known to cause turbine corrosion. Saturated steam
from individual HRSG drums should be checked to determine if contamination is due
to carryover. Elevated steam cation conductivities may be due to decomposition of
organic amines or reducing agents.
Specific conductivity is an inexpensive, reliable, on-line method for monitoring the
overall level of contamination, treatment chemicals and their trends.
The specific conductivity is dependent upon the form of the ion (i.e., whether it is in
salt, acid, or alkaline form). Therefore, the sensitivity of specific conductivity for
monitoring the overall level of the contaminants depends upon which contaminants are
present and in what form.
Specific Conductivity Target Values at Economizer Inlet(s). Specific conductivity at the
economizer inlet(s) can provide an indication of the ammonia level and pH during
normal operation, since other ionic impurity levels are relatively low. The specific
conductivity target value should, therefore, be consistent with the ammonia level.
Where applicable, specific conductivity of condensate polisher effluent may be
monitored (prior to chemical injection point) to assess performance.
Specific Conductivity Target Values in Makeup Water. The specific conductivity target
value is based on the sum of conductivities contributed by the individual ions at the
recommended effluent quality and by carbon dioxide. This target value should be
modified, if necessary, to be consistent with the capabilities of the makeup treatment
equipment design.
Specific Conductivity in HRSG Boiler Water. The measurement of specific conductivity
in the blowdown or downcomer of units on CT, PT or EPT provides an indirect yet

reliable on-line indication of the level of treatment applied to the system.
Contamination entering the heat cycle and the concentration resulting from
recirculation in the HRSG boiler water can be assessed by comparison of the
conductivity data to HRSG pH and phosphate values. In this way, operators can rely
2-31

on this measurement to initiate control measures to mitigate the undesirable effects

associated with increasing levels of contamination.
It should be kept in mind that samples taken from the downcomers will be diluted by
feedwater. Care should also be taken to ensure optimum sample flow rate and
temperature control(26).
As with other HRSG parameters, it is very important to customize these specific
conductivity limits for each HRSG drum boiler. This is included in the road map to
optimize phosphate chemistry for each drum unit in Section 3. If a boiler does not meet
these requirements then a series of tests/analyses should be undertaken to determine
the cause of the excessive contamination concentration level.
pH
Monitoring pH is necessary for the following reasons:
corrosion of metal is a function of pH,
alkaline pH values increase the stability of the magnetite film and reduce magnetite
solubility in water, and
alkaline pH increases the volatility of anions.
pH Target Values in HRSG Boiler Water. The boiler water pH for a unit utilizing
phosphate treatment is limited by the maximum phosphate concentration allowed

consistent with the target values for sodium concentration and sodium-to-phosphate
ratio and the ammonia concentration in the boiler water. Immediate shutdown for
drum units on AVT, PT, EPT and CT is recommended for low boiler water pH less than
pH 8 (7.5 OT units). Immediate shutdown is recommended since the pH will generally
be much lower locally under deposits or in high quality regions, and this could lead to
severe localized attack on HRSG tubes, particularly if the tubes have accumulated
deposits. In addition, immediate shutdown of units on CT should be considered if the
boiler water pH is greater than 10.0 out of concern for possible caustic gouging.
pH Target Values in Feedwater. The corrosion rate of carbon steel reaches minimal
values over the pH range of 9.2 to 9.6.

For units with condensate polishers in H-OH form, polisher run lengths decrease
significantly at higher pH values. Operation at the lower end of the feedwater pH
range may be necessary to maintain reasonable condensate polisher run lengths and
acceptable effluent quality when using hydrogen form cation resins.
2-32

Dissolved Oxygen (Non OT units only)

Monitoring of oxygen is necessary for the following reasons:
Copper alloy corrosion in the condenser (copper alloy tubes) is a function of oxygen,
carbon dioxide, and ammonia.
In deoxygenated feedwater systems, very low levels of oxygen (<<5 ppb) in

conjunction with high levels of hydrazine result in reducing conditions(12,17). Under
such conditions, the condensate/feedwater reacts with ferrous alloys in the
condensate/feedwater system to generate corrosion products. These corrosion
products are subsequently transported to the boiler, which may lead to increased
chemical cleaning requirements to avoid HRSG deposition related tube failures.
Flow-accelerated corrosion of carbon steel components can be accelerated by

overfeeding reducing agents (oxygen scavengers) and stopped by oxygen at
(24)
concentrations above 5 ppb . Overfeeding of reducing agents is, therefore, not
recommended and a few ppb of oxygen in high purity water may be beneficial in
reducing generation of iron oxides(12). (OT units do not feed hydrazine.)
Oxygen reacts synergistically with chloride to form local acid conditions that can
result in hydrogen damage(19).
Dissolved Oxygen Target Value at Economizer Inlet(s). This dissolved oxygen target
value is provided to minimize ingress of oxygen into the HRSG boiler and represents
an optimum level for feedwater train material corrosion.
Dissolved Oxygen Target Value at Deaerator Outlet. Monitoring of oxygen at the
deaerator outlet can serve as a check for the effectiveness of both deaeration and
chemical oxygen scavenging.
Dissolved Oxygen Target Value at Condensate Pump Discharge. This dissolved oxygen
target value is provided to minimize total corrosion in the feedwater piping.

Monitoring of oxygen at this point can provide feed forward control of the hydrazine
feed rate (if utilized), and provides a measure of condenser deaeration performance.
Dissolved Oxygen (OT Units)

For OT units it is necessary to measure dissolved oxygen in order to provide the proper
control of the oxygen feed rate. The cycle diagrams for OT (Sections 7 and 8) show
sampling points for dissolved oxygen at the condensate pump discharge, economizer
inlet, and boiler water (downcomer on drum units).
2-33

Sodium
Monitoring of sodium is necessary because sodium compounds such as sodium
hydroxide and sodium chloride are two major corrodents in the turbine, especially in
relation to stress corrosion cracking of some turbine blades and stainless steel
superheater tubes. Sodium hydroxide in steam from HRSGs has caused stress
corrosion cracking in turbines. Sodium hydroxide has in the past also caused gougingtype failure of boiler tubes in conventional fossil plants and in HRSGs subject to local
high quality or dryout conditions.
Sodium Target Value in Steam. The superheat and reheat steam sodium target value for
HRSG boilers on EPT, CT, AVT and OT is probably the least conservative limit in the
guidelines since all sodium present in the steam is assumed to be in a corrosive form
(NaCl, NaOH, etc.). There are no definitive experimental data for sodium hydroxide
concentration versus deposition, and the limit of 3 ppb Na is a best-judgment number
based on experience, but does not guarantee the absence of NaOH deposition in the LP
turbine. Thus, lower levels of sodium should be maintained if possible. Saturated
steam should be checked from each individual HRSG drum to determine if carryover is
a significant factor.
Recognizing that some of the sodium present in the steam with drum HRSG boilers on
PT will be in a noncorrosive form (sodium phosphate compounds), a higher sodium
limit (5 ppb) was selected for those units.
Sodium Target Value in HRSG Boiler Water (Drum Units). Boiler water sodium target
values were derived from sodium limits for the reheat/superheated steam for EPT, PT,
AVT and OT boilers.
The values for HRSG drum boilers on PT are consistent with conventional treatment
practice for lower pressure boilers but are lower than commonly maintained in practice
for higher pressure boilers. These lower values have been recommended not only in
consideration of turbine steam purity but also to reduce problems with phosphate
hideout during load changes. Lower sodium and consequently lower phosphate levels
have been found to reduce the severity of hideout. Although this practice gives less
buffering capacity in the HRSG boiler for contaminants introduced by condenser tube
leakage, adherence to the guidelines throughout the rest of the cycle will diminish the
need for excess buffering capacity. Phosphate levels consistent with the sodium target
values in the guidelines will provide adequate capacity when all other HRSG boiler
water target values are being met. Higher sodium and phosphate levels are permitted
by the action levels during excursions but are limited in duration, since these higher
levels only buffer boiler water pH and will not deter the carryover of corrodents such
as chlorides and sulfates into the turbine when their boiler water concentrations exceed
target values. For PT plants, out of the 5 ppb of sodium allowed in the steam, 2 ppb is
2-34

assumed to be associated with phosphate and 3 ppb is assumed to be sodium

hydroxide and other sodium salts.
For boilers on EPT, AVT and OT all sodium is assumed to be present in NaOH form.
Sodium hydroxide is more volatile than other sodium salts and thus provides a more
conservative estimate of vaporous carryover.
Sodium Target Value in Condensate and Makeup Water. Relatively low sodium levels
are required for condensate and makeup water for the following reasons:
to achieve recommended steam purity under normal operation without relying on

blowdown, leaving the full blowdown capability available to control transients and
maintain the chemistry within guidelines at all times,
to allow maximum flexibility during excursions, and
to provide protection for the combustion turbine if makeup water is used to control
NOx.
Limits on sodium concentration in the condensate are more relaxed for units with
condensate polishers than for units without polishers. Monitoring of the condensate
polisher effluent (where applicable) for sodium is useful in evaluating system
performance.
Sodium Target Value in Condensate Storage Tank Effluent (Aluminum Tank Only).
Corrosion of aluminum condensate storage tanks can occur in the presence of free
sodium hydroxide. Aluminum corrosion products form deposits in boiler tubes and on
turbine blades that are difficult to remove. Free sodium hydroxide will form in the
condensate storage tank whenever sodium levels become excessive. The major sources
of sodium in the condensate are from the makeup treatment system effluent and from
condenser leakage. The sodium level in condensate storage tank effluent should be
comparable to that in makeup treatment system effluent.
Phosphate (Drum HRSGs on PT and EPT)

Monitoring of HRSG boiler water phosphate is necessary because of the following
reasons:
the sodium-to-phosphate molar ratio determines the control point relative to the
pH/PO4 curves (Figure 2-2); and
acid phosphate corrosion is a concern for low sodium-to-phosphate ratios(7,8).
2-35

Corrosive conditions may result from the concentration of low ratio phosphate
treatment chemicals beneath porous magnetite and other boiler wall deposits, and in
steam blanketed areas. This may lead to tube damage by corrosion and lead to limiting
phosphate values within the pH-phosphate guidelines as determined by boiler water
samples from a HRSG boiler with accumulated waterside (porous) deposits. See
Section 1.10 for examples of acid phosphate corrosion in HRSG tubing.
Careful consideration should be given to avoid the feed of excessive amounts of
treatment chemicals in PT units. Possible deposit-phosphate reactions may be
occurring within and beneath porous deposits. Excessive phosphate feed may result in
corrosion damage to the tube metal through dissolution of the protective magnetite.
Many studies have now shown that the behavior under acceptably clean conditions
(EPRI Chemical Cleaning Guideline Values(23) and Figure 1-10) is very different than
when excessive deposits are present. The deposits are essentially magnetite but can
also contain other corrosion products from different pre-boiler construction materials.
Phosphate Target Value in HRSG Boiler Water for PT. Corresponding phosphate target
values at a sodium-to-phosphate molar ratio of 2.8 are included with the boiler water
sodium target values, as illustrated in Section 3. The phosphate provides good
buffering of acids and hydroxides and precipitates residual hardness, forming
removable sludge (hydroxyapatite). Phosphate strongly reacts with the oxides on
boiler tube surfaces (iron and nickel oxides) and these reversible reactions can cause
changes of boiler water pH, PO4 and OH concentrations. There are several mechanisms
of phosphate hideout and hideout return. These changes have historically not been
thought to cause any corrosion problems, but recently, with congruent phosphate
treatment (CPT), there have been a number of cases of severe acid phosphate corrosion
in conventional fossil plants(7,8) and in HRSG tubing (Section 1.10). It is now considered
good operating practice to avoid phosphate hideout and the associated need to add
treatment chemicals.
To avoid phosphate hideout, the tolerance of every boiler to the chosen phosphate
concentration should be tested during commissioning of the phosphate treatment and
during any monitoring campaigns to ensure optimum treatment levels (Section 9). The
test procedure consists of the following:
Select the Na and PO4 concentrations from Figure 3-2.
Feed tri-sodium phosphate to establish this concentration in the boiler water, if

possible, at a typical and high load for two hours each and calculate the material
balance around the boiler. If the phosphate is disappearing in the boiler, reduce
the injected feed to one half.
Measure Na, PO4 , and Na/PO4 molar ratios (theoretical and analytical) in the boiler
water at a steady load (typical and high). Whatever measured concentration of PO4
2-36

is determined, reduce it by about 20% and use this concentration as the established
normal limit.
Perform 1 weeks material balance to confirm this limit.
An alternative method to determine hideout and an equilibrium level is provided in

Figure 3-19 and associated discussion.
Use of PT should be evaluated carefully as phosphate hideout and carryover could
cause problems. One purpose of operating with EPT is to eliminate hideout.
Phosphate Target Value in HRSG Boiler Water for Equilibrium Phosphate Treatment.
The EPT method has been described previously, and additional information, including
the appropriate target values, can be found in Section 3. To convert a unit to EPT, the
equilibrium phosphate concentration must be determined experimentally. This
concentration will vary from HRSG boiler to HRSG boiler and also with operational
parameters, equipment changes and amount of waterside deposits on HRSG tube
surfaces. (Refer to Section 3 and Figure 3-19 for a complete guide for conversion to
EPT.)
The equilibrium phosphate concentration is determined by reducing unit load to a
minimum value, closing the boiler blowdown, and then adjusting the phosphate
concentration with tri-sodium phosphate to near the upper limit recommended for PT
for the boiler pressure utilized (see Section 3). The pH should be adjusted with sodium
hydroxide, if required, to 9.59.6, after correction for ammonia (see following
discussion) to ensure that some small concentration of free sodium hydroxide is present
(less than 1 ppm). The phosphate feed is then isolated and the unit ramped to full load.
Over the next several hours, the phosphate concentration will be reduced by hideout
within the HRSG boiler, finally reaching a plateau, which is the equilibrium
concentration. This then becomes the target phosphate concentration during normal
equilibrium operation. Utilizing phosphate levels above this concentration will result
in hideout.
During normal operation, the pH and phosphate concentrations should be observed
closely during rapid load reduction. As previously mentioned, the chemical
requirements of a unit will change over time. This can result in significant shifts in the
phosphate equilibrium concentration. If the required load changes needed for
observation do not occur during the course of normal operation, the unit should be
operated as required at three to six month intervals to obtain the necessary data and
make any needed changes in phosphate limits.
The sodium levels in the HRSG boiler water should be in accord with the
pressure/concentration curves (Section 3). The free sodium hydroxide should be
monitored and maintained in the range of 0.2 to 1.0 ppm as sodium hydroxide.
2-37

Effect of Ammonia. Boiler water pH is affected by ammonia or other amines at the
lower sodium and phosphate concentration recommended by the guidelines for higherpressure boilers. Although ammonia or other amines are very volatile, the level that
remains in the boiler water is sufficient to warrant consideration in the control of boiler
water pH. For example, the pH values vs. phosphate concentration at the sodium-tophosphate molar ratio of 2.8 with various ammonia levels are shown in Figure 3-6.
At boiler operating conditions, ammonia is associated and therefore does not contribute
to pH. However, at room temperature in the laboratory, ammonia dissociates and
biases the pH result to a higher value.
Each plant using PT or EPT at very low phosphate levels (less than 5 ppm) should
determine the effect of ammonia, amines or other additives on pH. The first step
would be to analyze the boiler water for the concentration of ammonia or amine
present. Then, the pH of synthetic solutions containing the desired phosphate
concentration and the prevalent ammonia or amine concentration are determined and
the proper correction established.
Silica
Monitoring silica is necessary for the following reasons:
precipitation of silica forms silicate deposits on the turbine that are not soluble in
water and are very difficult to remove; and
significant amounts of silica can enter the condensate/feedwater undetected in the

nonreactive colloidal form through the makeup, causing HRSG boiler water and
steam target values to be exceeded in spite of apparently good-quality makeup.
Silica Target Value in Steam. Based on the solubility of silica in superheated steam, a
limit of 10 ppb was chosen for units with reheat and 20 ppb was chosen for non-reheat
units. Compliance with these target values should limit deposition of silica in the
turbine. Saturated steam from each HRSG drum should be monitored as desired to
assess silica carryover.
In combined cycle units, the steam turbine is not the major component contributing to
efficiency, so some operators may decide to specify a higher silica target in steam.
Silica Target Value in HRSG Boiler Water. Vaporous carryover is the major contributor
to silica in steam(22). Figure 2-6 plots the distribution ratio, or concentration in the steam
to concentration in the boiler water, of silica as a function of pressure. High HRSG
boiler water pH will reduce silica carryover. This effect is insignificant for the pH
range used in higher pressure boilers and, for that reason, is not considered in these
2-38

guidelines. Boiler water silica concentration does not affect the distribution ratio
within the range of 10 to 1000 ppm, nor does the form in which silica enters the cycle(22).
Thus, there is no need to differentiate between EPT, CT, AVT, OT and PT. Operation at
higher boiler water pH values will cause these guidelines to be slightly conservative.
Silica Target Value in Condensate and Makeup Water. The target value of 10 ppb silica
in condensate is necessary for these reasons:
to achieve recommended steam purity under normal operation without relying on

blowdown, leaving the full blowdown capability available to control transients and
maintain the chemistry within guidelines at all times, and
to allow maximum flexibility during excursions.
For all units, the target value for makeup water is the same as that for the condensate;
however, this target value should be modified if necessary to be consistent with the
capabilities of the makeup treatment equipment design.
Chloride
Monitoring of chloride can be conducted because chloride contributes to the following:
corrosion fatigue, stress corrosion cracking, and pitting in LP turbines;
corrosion, hydrogen damage, and pitting in boilers; and
synergistic effect on corrosion in the presence of oxygen and copper oxide(19).
Chloride Target Value in Steam. Based on the solubility of sodium chloride in
superheated steam, a limit of 3 ppb is used for units with reheat and 6 ppb for nonreheat units. Compliance with these limits should result in avoidance of damage to the
boiler and turbine. These limits apply to EPT, PT, AVT and OT boilers.
Chloride Target Value in HRSG Boiler Water. Boiler water chloride target values were
derived from those for the reheat/superheated steam based on the mechanical
carryover (see Figure 2-5) and vaporous carryover (see Figure 2-6). These values were
found to be lower than those required to prevent boiler waterside corrosion. Therefore,
staying within these guidelines will protect both the HRSG boiler and the turbine.
For HRSGs operating with PT, it was assumed that chloride carries over as sodium
chloride. For EPT, AVT and OT units, it was assumed that chloride carries over in the
steam as a mixture of volatile and non-volatile ammonium compounds.
2-39

Work is presently being performed for EPRI by the Oak Ridge National Laboratory
(ORNL) to establish the volatility of salts under boiler operating conditions. This work
suggests that, under AVT, carryover of chloride is probably by hydrochloric acid, not
ammonium chloride(20). Calculations based on the partitioning constants measured in
this study can be made at this time giving the resulting composition of the vapor in
equilibrium with the boiler water at the target value limits. However, the relative
magnitude of these predicted values depends on temperature, HRSG boiler water
composition, and pH. The last is in turn dependent on the mathematical treatment
employed to provide the required total balance between cations and anions in the
water. This is not an artificial restriction as charge balance must be maintained in any
real solution, but it is the nature and relative concentrations of these counter ions that
can cause variations in the predicted pH at the boiling temperature in excess of one pH
unit. This magnitude of variation has profound effects on the composition of the vapor
and the resulting condensate, so that at present such calculations are better tested
against individual power plant chemistries to provide information as to the most
reliable method for assigning the relative concentrations of ions.
Chloride Target Value in Makeup Water. A makeup water target value of 3 ppb is
necessary for the following reasons:
to achieve recommended steam purity under normal operation without depending

on blowdown, leaving the full blowdown capability available to control transients
and maintain the chemistry within guidelines at all times, and
For all units, the target value for makeup water purity is the same as that for the steam;
however, this target value should be modified if necessary to be consistent with the
capabilities of the makeup treatment equipment design.
Sulfate
Monitoring of sulfate can be conducted for the following reasons:
sodium sulfate in combination with chloride contributes to turbine corrosion,
sulfate causes off-load corrosion of steam-side components(21), and
acid sulfate can cause turbine corrosion.
Grab sample analysis is normally used to assess sulfate.

Sulfate Target Value in Steam. Solubility of sodium sulfate in superheated steam is
estimated to be similar to that of sodium chloride, and acid sulfate is as corrosive as

2-40

acid chloride. Thus, the same limits were chosen for sulfate in steam as those for
chloride. This applies to all units.
Sulfate Target Value in HRSG Boiler Water. Boiler water sulfate target values were
derived from those for the reheat/superheated steam and the mechanical (Figure 2-5)
and vaporous (Figure 2-6) carryover. These values were found to be lower than that
required to prevent boiler waterside corrosion. Therefore, staying within these
guidelines will protect both the boiler and the turbine.
For the limits in this guideline, sulfate is assumed to carry over into the steam in the
form of ammonium sulfate in plants on AVT, OT and EPT. The distribution ratio of
ammonium sulfate was estimated based on the limited amount of data and is shown in
Figure 2-6.
Work is presently being performed for EPRI by Oak Ridge National Laboratory
(ORNL) to establish the volatility of salts under boiler operating conditions. This work
suggests that, under AVT, carryover of sulfate is probably predominantly as H2SO4, but
ammonium and sodium bisulfates are likely to contribute significantly to the carryover.
Calculations based on the partitioning constants measured in this study can be made at
this time giving the resulting composition of the vapor in equilibrium with the boiler
water at the target value limits. However, the relative magnitude of these predicted
values depends on temperature, boiler water composition, and pH. The last is in turn
dependent on the mathematical treatment employed to provide the required total
balance between cations and anions in the water. This is not an artificial restriction as
charge balance must be maintained in any real solution, but it is the nature and relative
concentrations of these counter ions that can cause variations in the predicted pH at
the boiling temperature in excess of one pH unit. This magnitude of variation has
profound effects on the composition of the vapor and the resulting condensate, so that
at present such calculations are better tested against individual power plant chemistries
to provide information as to the most reliable method for assigning the relative
concentrations of ions.
Boiler water sulfate was assumed to be mostly in the form of sodium sulfate for plants
using PT. The distribution ratio used is shown in Figure 2-6.
Sulfate Target Value in Makeup Water. The makeup water sulfate target value of 3 ppb
is necessary for the following reasons:
to achieve recommended steam purity under normal operation without relying

upon blowdown, leaving the full blowdown capability available to control
transients and maintain the chemistry within guidelines at all times, and

2-41

For all units, the target value for makeup water purity is the same as that for the steam;
however, this target value should be modified, if necessary, to be consistent with the
capabilities of the makeup treating equipment.
Sodium Hydroxide (Drum HRSGs on CT only)

Direct measurement of sodium hydroxide in the boiler water may be made by titration
of a sample of boiler water, or derived from the specific and cation conductivity. The
level of sodium hydroxide should be checked during initial operation on CT and as
needed during normal service to check and verify control by indirect methods.
Measurement and control of sodium hydroxide is needed on CT to prevent boiler
damage by caustic corrosion, and turbine damage by stress corrosion cracking.
Ammonia
Monitoring of ammonia supplements the direct measurement of pH and/or specific
conductivity for the control of the ammonia feed rate. Monitoring of pH due to
ammonia also enables determination of the correct boiler water pH, which is affected
by the ammonia concentration (see prior discussion).
Ammonia Target Values. The ammonia concentration should be consistent with the pH
requirements.
Reducing Agents such as Hydrazine (non OT units only)

Monitoring of hydrazine or other reducing agents (oxygen scavengers) at the deaerator
inlet or in the feedwater is necessary to provide feedback control of the hydrazine feed
rate. The hydrazine concentration at this location has an upper limit of 20 ppb since
there is evidence linking higher hydrazine concentrations and low oxygen levels at the
economizer inlet (<1 ppb) with flow-accelerated corrosion of the ferrous materials in
the HRSG boiler tubes and feedwater train(12).
It is necessary to advise that for preheaters constructed of all-ferrous materials, that
good operating practice requires that the need for a reducing agent addition is
confirmed by monitoring of the feedwater corrosion products and oxygen levels at the
economizer inlet(12). This is a key part of the feedwater optimization process discussed
in Section 9. Many utilities have found that additions of hydrazine in the all-ferrous
systems of conventional fossil plants make very little difference to the levels of both
oxygen and corrosion product transfer and have been able to eliminate its use(12). It has
also been found that hydrazine and other reducing agents concentrate in the LP HRSG
circuits to many times the value in the feedwater, producing a severe reducing
2-42

environment which may promote flow-accelerated corrosion. See the discussion of

FAC failures in HRSG tubing in Section 1.10.
Iron (and Copper, if Copper Alloys are Present)

Corrosion products will form deposits on HRSG tubes under high heat transfer
conditions, which can then trap and concentrate impurities, contributing to tube
failures by caustic gouging, hydrogen damage, and other forms of localized corrosion.
Dissolved iron can precipitate in the form of a magnetite or a substituted spinel because
of decreased solubility and/or possibly zeta or streaming potential effects at high
temperatures with high turbulence, such as that occurring in the regulating components
of the boiler or at heating surfaces subjected to high thermal loading(28).
If any HRSGs have feedwater systems with copper alloy heaters, it is necessary to
utilize a reducing agent treatment in order to maintain reducing conditions under
which copper transport activity is minimized. ORP monitoring can be used to
demonstrate the transition from oxidizing to reducing conditions which occurs at
startup of units that have not been protected by proper layup techniques.
Copper oxides act as oxidizers and sources of oxygen. Dissolved copper transported
from the condenser (copper alloy tubes) can deposit in the high-pressure turbine,
(29)
causing loss of turbine capacity and efficiency due to pressure and flow changes .
Total Iron and Copper Limits. The total iron target values are based on the minimum
values practically achievable and desirable from a corrosion and flow-accelerated

corrosion point of view. If copper is present in the systems, copper values should be
limited to 2 ppb.
Throughout the chemistry sections (3-8), the normal iron target levels (5 ppb) at the
economizer inlet have been chosen to correspond to EPRIs fossil plant cycle chemistry
guidelines(10,11,13,14), where there is extensive experience. It is recognized that HRSGs may
tolerate a larger iron level, despite the occurrence of many under-deposit HRSG
failures and active FAC (Section 1.10). These guidelines are regarded as interim, and it
is the intention to validate the target levels, including those for iron, based on
subsequent research and operating experience implementing these guidelines.
It should also be noted that for plants with air-cooled condensers having large
unalloyed steel surfaces, that the levels of iron in the feedwater may be considerably
higher than the guideline limits. It may not be possible to achieve less than 10 ppb
under these circumstances.
2-43

Oxidizing-Reducing Potential (ORP)

ORP surveillance is used to determine the condition of the feedwater. Positive ORP
values (> 0 mV) reflect oxidizing conditions while negative ORP readings are indicative
of reducing conditions. Monitoring ORP in addition to feedwater pH, specific
conductivity, chemical treatment levels and metals can be useful in optimization of
treatment (see Section 9).
Total Organic Carbon (TOC)

Organics can cause foaming in the HRSG drum, high mechanical carryover, and ion
exchange resin fouling, and may also affect the boiler and turbine corrosion, depending
on the specific species present. Organics form organic acids and carbon dioxide from
decomposition in the boiler and typically are detected by an elevation of cation
conductivity. Styrene sulfonic acids released from the oxidation of strong acid cation
resin in condensate polishers constitute a source of interference for sulfate by IC; they
can potentially contribute either as is, or as their pyrolysis products to corrosion
product generation, release and transport.
Condensate, and Makeup TOC Target Values. The target values are practical,
achievable values based on the limited amount of data available for plants using
ammonia and hydrazine. Plants using other, carbon-based amines for the control of pH
and/or oxygen may not be able to achieve these target values. If organic based
treatments are to be used, levels of TOC and their effects on cation conductivity should
be determined during commissioning and the monitoring campaigns discussed in
Section 9 to develop the optimum treatment. Since the contribution of the
decomposition products of all the various carbon-based amines to cycle corrosion has
not yet been determined, the target values have not been modified for units using these
chemicals.
Air In-Leakage
Air in-leakage is the primary source of oxygen and carbon dioxide in the condensate
and feedwater system. Oxygen and carbon dioxide can promote corrosion, and carbon
dioxide can degrade condensate polisher performance. High air in-leakage rates can
also cause corrosion of the condenser shell and can reduce condenser vacuum, reducing
the efficiency of the cycle.
Air In-Leakage Limit. The design maximum air in-leakage rates recommended by the
Heat Exchange Institute (HEI) are shown in Figure 2-7. Condenser air removal sections
are typically designed to meet these values. Therefore, condenser air in-leakage in
excess of design generally exceeds the capacity of the air removal system, resulting in
an increase in condensate dissolved oxygen levels. The air in-leakage target value of 1
2-44

scfm/100 MW (1.7 sm3/h/100 MW) was selected to provide a practical and simple
guide based on the HEI data.
Dissolved O2 in condensate (ppb)
50
HEI air removal capacity (scfm)

20
Attainable with 20
to 40 scfm air
removal capacity
Attainable with up to 20
scfm air removal
capacity
40
40
Unattainable
regardless of air
removal capacity
30
20
10
HEI 7 ppb guarantee
0
0
10
15
20
25
Air In-leakage (scfm)

Figure 2-7
Influence of Air In-Leakage and Installed Air Removal Capacity on Achievable
Dissolved Oxygen Levels in the Condensate (1scfm = 1.7sm3/h)
Source: Guide to the Design of Secondary Systems and Their Components to
Minimize Oxygen-Induced Corrosion, Palo Alto, California: Electric Power
Research Institute, March 1982. EPRI NP-2294.
2-45

2.8 GUIDELINE CUSTOMIZATION AND OPTIMIZATION

Ideally, cycle chemistry control customization and optimization will start in the design
phase. The actual cycle characteristics should be determined during commissioning,
which would lead to customization of these guidelines.
Customization and optimization of the cycle water and steam chemistry is thoroughly
discussed in Section 9 and includes the following steps:
selection of unit specific feedwater treatment,
selection of unit specific HRSG boiler water for each pressure cycle,
determination of optimum unit specific control limits and alarm settings,
selection of unit specific cycle chemistry process/control equipment,
development of operating guidelines (Episodes of contamination ingress must be

dealt with quickly. The source of contamination should be eliminated and any
repairs made as soon as possible. Procedures should detail what is to be done in a
clear and concise way.),
determination of sampling and instrumentation requirements,
commissioning,
specification of shutdown and layup practices, and
determination of optimum chemical cleaning criteria.
2.9 REFERENCES
1. D. Dutina, A Survey of Modern Boiler Water Practice: Boiler Water Control to
Minimize Corrosion of the Steam Generators in the Clinch River Breeder Reactor
Plant, GEAP-14042 UG-79H, April 1975, U.S. Energy Research and Development
Administration Contract at (04-3)-893 Task 10, pp. 7, 8.
2. H. A. Klein, Use of Coordinated Phosphate Treatment to Prevent Caustic Corrosion
in High Pressure Boilers, Combustion, October 1962, pp. 4552.
3. S. F. Whirl and T. E. Purcell, Protection Against Caustic Embrittlement by
Coordinated Phosphate-pH Control, Engineers Society of Western Pennsylvania,
Water Conference Proceedings, 1942, p. 45.
4. F. J. Pocock and J. A. Lux, Waterside Corrosion in Fossil-Fired Steam Generators,
Corrosion 79-T-HA Symposium on the Effect of Water Chemistry on Corrosion
Induced Failures in Power Systems, National Association of Corrosion Engineers,
Atlanta, Georgia, March 1216, 1979.
2-46

5. H. A. Klein, et al., A Field Survey of Internal Boiler Tube Corrosion in High

Pressure Utility Boilers, Proceedings of the American Power Conference, Vol. 33,
1971, pp. 702709.
6. V. M. Marcy and S. L. Halstead, Improved Basis for Coordinated Phosphate pH
Control of Boiler Water, Combustion, January 1964, pp. 4547.
7. a) Metallurgical Guide for Boiler Tube Failures, Electric Power Research Institute, Palo
Alto, Calif., TR-102433, October 1993.
b) R. B. Dooley and S. Paterson, Phosphate Treatment: Boiler Tube Failures Lead
to Optimum Treatment, IWC Paper-94-50, International Water Conference,
Pittsburgh, Pa., October 31/November 2, 1994.
8. R. B. Dooley and W. P. McNaughton, Boiler Tube Failures: Theory and Practice. Three
Volume Book, Electric Power Research Institute, Palo Alto, Calif., EPRI Book TR105261, 1996.
9. G. V. Vasilenko, G. P. Sutotsky and R. B. Dooley, Investigation and Operating
Experience of Russian High Pressure Drum Boilers Using Phosphate Treatment, Electric
Power Research Institute, Palo Alto, Calif., TR-104008, April 1994.
10. M. Ball and R. B. Dooley, Sodium Hydroxide for Conditioning the Boiler Water of Drum
Type Boilers, Electric Power Research Institute, Palo Alto, Calif, TR-104007,
RP 9000-20.
11. Cycle Chemistry Guidelines for Fossil Plants: Phosphate Treatment for Drum Units.
Electric Power Research Institute, Palo Alto, Calif., EPRI TR-103665, December 1994.
12. R. B. Dooley, J. Mathews, R. Pate and J. Taylor, Optimum Chemistry for AllFerrous Feedwater Systems: Why Use an Oxygen Scavenger?, 55th Annual
Meeting, International Water Conference, Pittsburgh, Pa., Oct. 31Nov. 2, 1994.
13. Cycle Chemistry Guidelines for Fossil Plants: All-Volatile Treatment. Electric Power
Research Institute, Palo Alto, Calif., TR-105041, April 1996.
14. Cycle Chemistry Guidelines for Fossil Plants: Oxygenated Treatment. Electric Power
Research Institute, Palo Alto, Calif., TR-102285. December 1994.
15. Interim Consensus Guidelines on Fossil Plant Cycle Chemistry, CS-4629, Electric Power
Research Institute, Palo Alto, Calif., June 1986.
16. Guideline Manual on Instrumentation and Control for Fossil Plant Cycle Chemistry.
Electric Power Research Institute, Palo Alto, Calif., CS-5164, April 1987.
2-47

17. Monitoring Cycle Water Chemistry in Fossil PlantsVol. 3, Electric Power Research
Institute, GS-7556, Palo Alto, Calif., October 1991.
18. Cycle Chemistry Corrosion and Deposition: Correction, Prevention and Control, Electric
Power Research Institute, Palo Alto, Calif., TR-103038, December 1993.
19. 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. 3238.
20. Behavior of Ammonium Salts in Steam Cycles, Electric Power Research Institute, Palo
Alto, Calif., TR-102377, December 1993.
21. Chemical Control of the Steam Water Circuit of Drum-Type and Once-Through
Boilers, Advisory Panel on Water Chemistry Management, CEGB Generation
Operation Memorandum 72Part 2, April 1983.
22. E. E. Coulter, E. A. Pirsh, and E. J. Wagner, Jr., Selective Silica Carry-Over in
Steam, Transactions of the ASME, May 1956, pp. 869873.
23. Guidelines for Chemical Cleaning of Fossil-Fueled Steam Generating Equipment, Electric
Power Research Institute, Palo Alto, Calif., TR-102401, June 1993.
24. F. J. Witt, Prepared Discussion of Erosion Corrosion in Power Plants, in
Proceedings of the International Water Conference, October 1989, pp. 147148.
25. On-Line Conductivity Measurements, ASTM D-4519, Vol. 1101, 1102, ASTM
Annual Standards Book on Water.
26. ASTM D-5540, ASTM Vol. 1101, 1102, Annual Standards Book on Water.
27. Turbine Steam, Chemistry, and Corrosion, Electric Power Research Institute, Palo Alto,
Calif., EPRI TR-103738, August 1994.
28. VGB Guidelines for Boiler Feedwater, Boiler Water and Steam for Water Tube
Boilers with a Pressure of 64 Bar and Higher, VGB Kraftwerkstechnik 60, No. 10,
October 1980, pp. 714721.
29. O. Jonas, Transport of Chemicals in Steam Cycles, Presented at EPRI Symposium
on Fossil Plant Water Chemistry, June 1985.
2-48
3
CYCLES WITH DRUM HRSGs ON PHOSPHATE AND
EQUILIBRIUM PHOSPHATE TREATMENT (PT AND
EPT)
3.1 INTRODUCTION TO EPT AND PT

An overview of the phosphate and equilibrium phosphate treatment philosophies was
given in Section 2. This Section provides cycle chemistry target values and action levels
for each monitoring point for combined cycle plants having HRSG drum boilers on
phosphate treatment (PT) and equilibrium phosphate treatment (EPT). This section is
intended to be used by operating staff and management personnel.
To determine whether a particular HRSG drum cycle should be operated on EPT or PT,
the reader is first referenced to Section 9, and advised to follow the HRSG Boiler Water
Selection procedure outlined in the road map (Figure 9-5).
In Section 1 mention is made of the fact that combustion turbine/combined cycles are
available in a multitude of designs and configurations. Because of the many varieties
of cycles presently available and those under development, it is not possible to include
each in these guidelines. The cycle diagram which was chosen for the presentation of
target values and action levels for drum units is one of the more complex available,
having three drums, each operating at a different pressure (low, intermediate and
high). These cycle diagrams are presented in Figure 3-1 (PT) and Figure 3-12 (EPT).
Only reheat cycles are included; however, non-reheat units are addressed in
subsequent parts of this Section.
Reheat and superheated (main) steam chemistry target values established in the EPRI
report Cycle Guidelines for Fossil Plants: Phosphate Treatment for Drum Units(1) adequately
protect the steam turbine and the rest of the heat cycle from corrosion or deposition. In
recognition of this fact, PT and EPT limits were set for reheat and superheat steam in
this document for PT and EPT treated HRSG units.
3-1

Cycles with Drum HRSGs on Phosphate and Equilibrium Phosphate Treatment (PT and EPT)
The principles established in this Section should serve as guidelines regardless of the
cycle diagram configuration for which chemistry target values are to be established.
For example, as discussed in Section 1.11, some cycles will not have preheaters or
deaerators. Suitable adjustments must be made in establishing chemistry target values
for these cases.
Also, in some cycles, the low and/or intermediate pressure superheated steam may not
be utilized in the steam turbine, but is used instead for cogeneration, NO x control or for
some other purpose. In such cases, the chemistry target values for this steam must be
established to meet the requirements of the intended end use, whatever that might be.
3.2 GUIDELINES FOR PHOSPHATE TREATMENTS

Target values and action levels for all key cycle contaminants for HRSG drum boilers
are presented as a continuum over a broad range of operating pressures in Figures 3-2
through 3-5; and 3-13 through 3-16. As mentioned in Section 2, cycle contaminant
values for the minimum HRSG boiler pressure of 600 psi (4.1 MPa) depicted on these
curves should be used for all boilers operating at 600 psi (4.1 MPa) and below. This is
based on the rationale that:
There is considerable uncertainty in values extrapolated from the ray diagram

(Figure 2-6) at pressures below 600 psi (4.1 MPa).
The contaminant values at 600 psi (4.1 MPa) provide conservatism for boilers
operating at 600 psi (4.1 MPa) and below.
For PT and EPT units there is no need to add additional phosphate above those
levels designated at the 600 psi (4.1 MPa) pressure.
3.3 TARGET VALUES FOR HRSGs WITH REHEAT ON PT

The sample points, monitoring parameters, target values, and action levels were
developed for those plants that have reheat. The following figures show the target
values and action levels for each sample point and monitoring parameter:
cycle chemistry diagram (Figure 3-1);
HRSG boiler water limits (it should be noted that these limits and curves are
provided for troubleshooting, commissioning, and for the monitoring campaigns
described in Section 9.5):
3-2
sodium and phosphate versus operating pressure (Figure 3-2),
chloride versus operating pressure (Figure 3-3),

sulfate versus operating pressure (Figure 3-4),
silica versus operating pressure (Figure 3-5),
pH versus phosphate at various ammonia levels (Figure 3-6),
pH versus ammonia at various carbon dioxide concentrations (Figure 3-7).
(A discussion relative to the need for adjusting HRSG boiler water pH for the presence
of ammonia is given in Section 2.7.)
An indirect method of determining phosphate concentration in the boiler water is
through the use of specific or cation conductivity. Figure 3-8 gives the specific
conductivities of pure sodium phosphate solutions at molar ratios of 1.5, 2.0, 2.6 and
3.0. The use of caustic and ammonia will increase specific conductivity above that
shown in Figure 3-8. Plant specific curves for specific conductivity to reflect caustic
and ammonia concentrations in actual usage can be determined experimentally in a
manner similar to that for determining the effect of ammonia on pH as outlined in
Section 2. Increases in conductivity above this experimentally determined baseline
curve reflect contamination by other ions, notably chloride and sulfate.
The use of cation conductivity has the advantage of removing the effects of both
ammonia and caustic from the conductivity measurement. The conductivity of pure
phosphoric acid (H3PO4) is also shown on Figure 3-8. On this line lie the conductivities
of all sodium phosphate solutions after cation exchange, and is independent of the
molar ratio of sodium to phosphate. This curve could serve as a baseline for cation
conductivity vs. phosphate concentration. Values above the baseline will again reflect
boiler impurities, particularly chlorides and sulfates, which will now be magnified
through the use of cation conductivity as compared with specific conductivity.
Figure 3-8 can be used in conjunction with Figure 3-2 to establish the relationship of
phosphate vs. drum boiler pressure. For example, if the cation conductivity of the
boiler water is 24 S/cm, the H3PO4 curve (Figure 3-8) indicates there is approximately
6 ppm of phosphate in the boiler, in the absence of chloride or sulfate contamination.
This will locate a point on Figure 3-2 Boiler Water Sodium and Phosphate vs.
Operating Pressure.
A series of curves were developed through the combined use of Figure 3-2, Sodium
and Phosphate vs. Operating Pressure and Figure 3-8 Specific Conductivity vs.
Phosphate Concentration at Various Sodium to Phosphate Molar Ratios and of
Phosphoric Acid. By combining these two curves, it is possible to relate specific and
cation conductivity to boiler operating pressure. The following curves present these
relationships:
3-3

Specific Conductivity vs. Pressure

3.0 molar ratio Na:PO4 (Figure 3-9)
Cation Conductivity vs. Pressure

3.0 molar ratio Na:PO4 (Figure 3-10)
As previously mentioned, these specific and cation conductivity curves are for pure
boilerwater uncontaminated with chlorides or sulfates. The specific conductivity
curves should be corrected for ammonia. Also, values of Na:PO4 molar ratio above
three indicate free caustic (or possibly contamination with sodium salts), and this
requires a correction for specific conductivity. So it should be emphasized that these
curves are valid only for Na:PO4 ratio of 3:1. To obtain a reliable indication of the
presence of contaminating anions (chloride and sulfate), it will be necessary to know
the concentrations of Na and PO4 to determine the Na:PO4 ratio, and the PO4
concentration to correct the cation conductivity to get a reliable indication of chloride
and sulfate.
Sodium hydroxide and ammonia do not affect cation conductivity, and excess sodium
above a molar ratio of 3.0 must be measured in another way to detect free caustic.
As it is suggested that the specific and cation conductivity measurements of the HRSG
boiler water are used as the primary chemistry control, they can be utilized together
with other heat cycle monitored parameters to diagnose effectively various potential
operational problems. For example, from a baseline steady load and uniform HRSG
boiler water specific and cation conductivity, a sudden or continuing change in either
or both of these parameters can be the basis for determining the source of the potential
problem and of initiating the appropriate corrective action. The following four case
studies illustrate the diagnostic indications.
Case I: HRSG Boiler Water Specific Conductivity Rises While Cation Conductivity
Remains Steady
A. Ammonia feed increasing
1. pH at economizer inlet increases
2. HRSG boiler water pH increases
A. Sodium hydroxide feed increasing
A. Sodium hydroxide cycle contamination
3-4

4. Makeup specific conductivity and condensate pump discharge sodium

increasemakeup system malfunction
5. Condensate polisher effluent sodium and economizer inlet pH increase
condensate polisher malfunction
Case II: HRSG Boiler Water Specific Conductivity Falls While Cation Conductivity
Remains Steady
A. and B. Same as Case I, except parameters fall
Case III: HRSG Boiler Water Specific Conductivity and Cation Conductivity Both
Rise
A. Phosphate feed increasing
1. HRSG boiler water pH and phosphate increases
A. Cycle contamination
2. Makeup specific conductivity increasesmakeup system malfunction
3. Condensate pump discharge cation conductivity and sodium increases
condenser leak and/or makeup system malfunction
4. Condensate polisher cation conductivity increasespolisher malfunction
5. Economizer inlet cation conductivity increasesreflects 1., 2., and 3. above
6. HRSG boiler water pH dropsacid contaminationmakeup and/or polisher
malfunction (economizer inlet pH drops); brackish water intrusion
Case IV: HRSG Boiler Water Specific and Cation Conductivity Both Fall
A. Phosphate feed decreasing
1. HRSG boiler water pH and phosphate drop
A varying unit load may add a complication to these diagnostic procedures related to
possible chemical hideout. In this situation, additional monitoring may be required to
verify the underlying root causes for chemistry parameter deviations from their normal
target values.
Copies of Figure 3-1 through 3-5 and Figures 3-9 and 3-10, modified if necessary to
reflect specific unit characteristics as explained in Section 2 and/or experience, should
be included in the plant operating procedures and prominently displayed in the control
room, water and steam sample room, and chemistry laboratory. It may be more
convenient to develop a separate figure, based on Figure 3-1, which only includes the
core parameters for the specific HRSG unit.
3-5

Economizer Inlet and Attemperation Water
Target
Sample
Cation conductivity, S/cma

Oxygen, ppb
(switchable with CPD)
0.2
0.35
0.65
> 0.65
1-10
> 15
> 20
pH, pH unitsa
9.2-9.6
< 9.2
> 9.6
W
C or S
< 20
>5
To -300
To +50
Parameter
**
Iron, ppb
Hydrazine, ppb (if used)
With oxygen
scavenger
ORP, mV
Without oxygen
scavenger
Saturated Steam
Parameter
Target
Superheat & Reheat Steam

Sample
Cation conductivity,
S/cma
0.3
0.55
1.0
> 1.0
Silica, ppb
10
20
40
> 40
Sodium, ppb
10
20
> 20
Target
Parameter
*
*
Deaerator
Sample
Sodium, ppb
10
20
> 20
S/cma
0.3
0.55
1.0
> 1.0
HP SH steam
IP SH steam
IP SH steam
LP SH steam
Chemical
feed
Chemical
feed
LP
drum
Flue gas
to stack
Chemical
feed
IP
drum
Reheater
HP
drum
HP

To steam injection
(if used)
IP
LP
Steam turbine

Target
Parameter
Sample
>1
Air inleakage,
SCFM/100 MW
Condenser Leak Detection Trays or

Hotwell Zones (If applicable)
Target
Parameter
Heat Recovery
Steam
Generator (HRSG)
Sample
S/cma
Condenser
Flue gas
Deaerator
pump
*
*
*
Low
pressure
(LP) section
LP
blowdown
Boiler Water
(Blowdown or Downcomer)
Sample
Immediate
Shutdown
Phosphate, ppm
c
c
pH, pH unitsa
<8
Sodium, ppm
Sililca, ppb
Parameter
Preheater
Target
Specific or cation
conductivity, S/cma
Intermediate
pressure
(IP) section
IP
blowdown
Supplemental
firing (if used)
Air Fuel
High
pressure
(HP) section
HP
blowdown
Attemperation
feed
Feedwater
pump
Chemical
feed
Combustion
Electricity
turbine and
generator
Water
Steam injection
injection
from IP steam
Bypass
Condensate
polisher
(if used)
Target
*
*
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
Condensate Polisher Effluent (If applicable)

Parameter
*
Footnotes
Sample Frequency
Target Values
C = continuous
S = grab, once per shift
D = grab, once per day
W = grab, weekly
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

b = See curves of maximum allowable concentration versus pressure
c = Must be determined
10
Specific conductivity,
S/cma
0.1
T or W
300
Condensate
pump
Cumulative Hours per Year

N (Normal)
Makeup
system
Condensate
storage
Parameter
Base Load
Sample
Silica, ppb
Total organic carbon, ppb
Maximum Annual Exposure to

Contaminant Conditions
Targets
Parameter
Target
Sample
S/cma
0.2
> 0.2
Sodium, ppb
10
20
> 20
*
*
Target
Plants with
polisher
Plants without
S/cma
polisher
Oxygen, ppb (switchable with EI)
Plants with
polisher
Sodium, ppb
Plants without
polisher
Sample
0.3
> 0.3
0.2
0.35
0.65
> 0.65
20
40
> 40
10
> 10
10
20
> 20
T or W
200
> 200
Sample and Chemical Feed Identification
= Core parameter
= Continuous samples
= Chemical feed
Figure 3-1
Cycle Chemistry Diagram for an HRSG Drum Unit on Phosphate Treatment (Plants With Reheat). It should be noted that this diagram does not represent exactly any operating unit. It is only illustrative for use in
the chemistry cycle diagrams for drum type HRSG units. Operators should apply the parameters/target boxes to their actual unit. These may need customization according to Sections 1.11 and 9.5.
3-7

Drum Pressure (MPa)

6.2
7.6
9.0
10.3
11.7
13.1
14.5
15.8
17.2 18.6 19.6

40
30
20
Action level 3
20
10
9
8
7
6
Action level 2
10.0
9.0
8.0
Sodium (ppm Na)
7.0
6.0
4
Action level 1
5.0
3
4.0
3.0
2
Normal
2.0
1.0
0.9
0.8
0.7
0.6
1.0
0.9
0.8
0.7
0.6
0.5
0.4
Corresponding phosphate at sodium-to-phosphate ratio of 2.8 (ppm PO4)
4.8
30
0.5
0.3
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 3-2
Phosphate Treatment: Boiler Water Sodium and Phosphate vs. Operating
Pressure (HRSG/Combined Cycle Plants With Reheat)
3-9

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
10
9
8
7
6
Action level 3
Action level 2
5
4
3
Chloride (ppm Cl)
Action level 1
2
Normal
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 2700 2850
Figure 3-3
Phosphate Treatment: Boiler Water Chloride vs. Operating Pressure
(HRSG/Combined Cycle Plants With Reheat)
3-10

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
Action level 3
10
9
8
7
Sulfate (ppm SO4)
6
5
Action level 2
4
3
Action level 1
2
Normal
1.0
0.9
0.8
0.7
0.6
0.5
600 700 900
1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
Figure 3-4
Phosphate Treatment: Boiler Water Sulfate vs. Operating Pressure
3-11

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
20
15
10
8
7
6
5
4
3
Silica (ppm SiO2)
Action
level 3
1.0
0.8
0.7
0.6
0.5
Action
level 2
0.4
Action
level 1
0.3
0.2
Normal
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 3-5
Phosphate Treatment: Boiler Water Silica vs. Operating Pressure
3-12

10.1
10.0
9.9
9.8
9.7
9.6
9.5
pH at 25 C
9.4
1.0 ppm NH3

(Na/PO4 = 2.8)
9.3
0.5 ppm NH3
9.2
9.1
0.3 ppm NH3
9.0
8.9
0.1 ppm NH3
8.8
8.7
8.6
0 ppm NH3
8.5
8.4
0.1
1.0
10
20
Phosphate (ppm PO4)

Source: Unpublished NUS Corporation Data
Figure 3-6
Phosphate Treatment: HRSG Boiler Water pH vs. Phosphate at Various Ammonia
Levels
Source: Unpublished NUS Corporation Data
3-13

Ammonia (ppm NH3)
10
2.0
1.0
1.0
pm
CO
CO
pm
pp
CO
0.5
CO
pm
0.1
8.8
9.0
9.2
9.4
9.6
9.8
10.0
pH at 25 C
Source: Adapted from unpublished NUS Corporation data
Figure 3-7
Phosphate Treatment: Ammonia Concentration vs. pH for Various Carbon Dioxide
Concentrations
Source: Adapted from unpublished NUS Corporation Data
3-14

Specific Conductivity S/cm)
50
Vmol 3.0
40
H3PO4
30
Vmol 2.6
20
Vmol2.0
Vmol1.5
10
0
0
10
-3
4
Phosphate (ppm PO )
Figure 3-8
Phosphate vs. Specific Conductivity at Various Na to PO4 Molar Ratios (Vmol) and
as Phosphoric Acid(2) (The H3PO4 curve represents all sodium phosphate ratios
after cation exchange.)
3-15

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
190
180
170
160
150
Action level 3
140
130
Specific Conductivity, S/cm
120
110
100
90
80
Action level 2
70
60
50
40
Action level 1
30
Normal
20
10
0
600 700
900 1100 1300 1500 1700 1900 2100 2300 2500 2700 2850
HRSG Drum Pressure, psia
Figure 3-9
Phosphate Treatment (PT) HRSG Drum Water Specific Conductivity vs. Operating
Pressure. Molar Ratio Na:PO4 = 3.0 (Plants With Reheat)
3-16

Drum Pressure (MPa)
4.8
6.2
7.6
9.0
10.3
11.7
13.1
14.5
15.8
17.2
2300
2500
18.6 19.6
150
140
130
Action level 3
120
110
Cation Conductivity, S/cm
100
90
80
70
Action level 2
60
50
40
Action level 1
30
20
Normal
10
0
600 700
900
1100
1300
1500 1700
1900 2100
2700
2850
Figure 3-10
Phosphate Treatment (PT) HRSG Drum Water Cation Conductivity vs. Operating
Pressure. Molar Ratio Na:PO4 = 3.0 (Plants With Reheat)
3-17

3.4 TARGET VALUES FOR PLANTS WITHOUT REHEAT ON PT

established for those plants that do not have reheat. While this section does not include
separate cycle diagrams with these values, the following will provide guidance for the
determination of proper operating values:
For the concentration values vs. pressure curves (Figures 3-2 through 3-5), the
values for concentration for non-reheat units are twice those for reheat units.
The target values (Figure 3-1) do not always reflect a 2:1 ratio (non-reheat:reheat).
Differences between the normal action level for reheat and non-reheat units are
shown in Table 3-1. Values not listed in this table are identical for reheat and nonreheat units.
Table 3-1
Differences Between Normal Action Levels for Reheat and Non-Reheat HRSG Units on PT
Sample Point
Condensate Pump
Discharge
Parameter
Reheat
Non-Reheat
with Polisher
10
20
without Polisher
10
with Polisher
0.35
0.3
without Polisher
0.25
0.2
0.2
0.25
10
Sodium, ppb
Cat. Conductivity, S/cm
Condensate Polisher
Effluent
Sodium, ppb
Economizer Inlet
0.2
0.25
Saturated Steam
0.3
0.35
Silica, ppb
10
20
Sodium, ppb
10
Sodium, ppb
10
0.3
0.35
RH/Main Steam
3-18

3.5 NORMAL OPERATION FOR PT

Phosphate Hideout and Its Control
With PT, the phosphate during normal operation should be at a level that the HRSG
can maintain without hideout. The procedures described later in this Section to
determine the equilibrium level for EPT can also be used for PT.
Hideout may be expected during initial startup on PT. This is related to the so called
seasoning of the HRSG boiler tube surfaces (protective magnetite film formation) and
possible chemical concentrations beneath any remaining water-side deposit
accumulations. Once these conditions are satisfied, the phosphate concentration in the
HRSG boiler water should stabilize. It is important to be patient during this period and
not to chase phosphate while attempting to maintain pH-phosphate control
relationships.
As indicated in Figure 3-11, the control range (pH-phosphate) for PT has been enlarged
over that for congruent phosphate treatment (CPT) and there is an allowance for up to
one ppm of free sodium hydroxide (NaOH) over a given range of phosphate not to
exceed that dictated by HRSG boiler pressure. The procedures to assess phosphate
hideout are provided in Section 2. No addition of the more acidic mono- and disodium phosphates should be made to correct for any observed hideout. Controlled
additions of tri-sodium phosphate can be made to increase phosphate concentration
levels materially affecting pH. Minor sodium hydroxide additions to give boiler water
concentration of always less than one ppm (free sodium hydroxide beyond the
Na/PO4 ratio of 3.0) can be utilized to increase pH if it becomes necessary, but should
be avoided, if possible. It is important to have knowledge about the typical amounts of
chemicals that can be added to the boiler. Normally, hydrated tri-sodium phosphate
(Na3PO412H2O) and di-sodium phosphate (Na2HPO47H2O) are utilized because of
their better solubility as compared with the anhydrous (Na3PO4; Na2HPO4) materials.
Any additions should be made based on the targeted sodium to phosphate ratio. The
concentration range may be up to 10 ppm PO4 but is dependent on what the HRSG will
accept at the operating pressure utilized.
Required additions of treatment chemicals are shown below for each ppm of phosphate
to be attained in the HRSG boiler water. Total additions should be based on the normal
operating HRSG boiler water volume for the particular boiler, and the desired Na/PO 4
ratio as shown below. The bottom line is, of course, what the ratio is in the boiler
water:
3-19

ppm PO4
1.0
1.0
1.0
Na/PO4 Ratio
2.8
2.9
3.0
g. Na3PO412H2O/
1000 lbs H2O
1.45 g
1.63 g
1.63 g
g. Na2HPO47H2O/
1000 lbs H2O
0.26 g
0.13 g
0
Careful records of the chemical additions should be kept. With the blowdown valve
normally closed, the only additions required should be for average carryover and
sample losses (<0.5%).
It is advisable to use good technical grade chemicals (such as specified by the American
Chemical Society or equivalent). Any sodium hydroxide utilized should be of a grade
specified by ASME PTC-31 (or equivalent and which is usually used for regeneration of
condensate polishing resins). The latter (as crystalline material) should be stored in a
dry atmosphere as it readily absorbs moisture from humid environments. Since
operation should normally be with the blowdown valve closed or nearly closed, careful
control of the inventory of chemicals added must be maintained to ensure that
additions are not being made to correct for phosphate hideout.
Blowdown is to be utilized only for contaminant control. It may, and should, be
heavily employed if suspended corrosion products are in the HRSG boiler water
during startup. Load should not be increased above 50% with any observable
suspended oxide in the boiler water. This can be monitored semi-quantitatively with
membrane filter charts(3).
Reaction to Contaminants in Boiler Cycle

Condenser cooling water in-leakage or makeup water contamination can and will
occur. The reaction to this is dependent on the kind of contamination. Three examples
could be:
chloride or sulfate excursions due to condenser in-leakage;
caustic or acid contamination from makeup (or condensate polisher if utilized)

regenerant chemical leakage or
silica from extraneous sources
3-20

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
0.2
8.5
5
ppm PO4
Equivalent NaOH Concentration (ppm)
3.0
10
Figure 3-11
Schematic of Operating Ranges of Boiler Water on Equilibrium Phosphate
Treatment (PT)
The reaction in all cases should be to increase blowdown, necessitating HRSG boiler
water treatment chemical addition to compensate for the loss, and in some cases
variation of additions to correct for such things as pH depression (caustic addition).
Such caustic injection should never result in the HRSG boiler water caustic
concentration exceeding 1 ppm. Mono-sodium or di-sodium phosphate may have to be
added to neutralize any caustic in-leakage; this is the only case in which mono-sodium
phosphate should be utilized.
Startup and Shutdown Operation

During startup the effect of chemistry control impacts on the potential for internal
boiler deposits and related corrosion(4). Focus should be directed towards the
identification and correction of the root causes of chemical control problems as follows:
Cold Start. The ramp to full pressure is dependent on the HRSG design and the
HRSG/turbine stress limitations. Frequent analysis of the HRSG boiler water with
emphasis on suspended solids and silica is recommended. Suspended solids is a
measure of the magnetite inventory and the source of deposition and subsequent
under-deposit corrosion. Silica is monitored out of concern for turbine deposition.
3-21

Adjust HRSG boiler chemical feed to take advantage of tolerance for higher
alkalinity at lower pressure.
Adjust phosphate feed to support anticipated HRSG boiler blowdown rate. The use
of conductivity measurements (specific or cation) will provide an indirect
assessment of the phosphate concentrations as previously described.
Anticipate startup and begin pumping chemicals so that target treatment is in place
when the HRSG is put on line.
Maximize HRSG blowdown and perform bottom blow during startup when solids
are at their highest concentration.
When pressure increases to near operating range the phosphate residual should be
allowed to slide back to a concentration consistent with the guidelines values for
PO43 versus pressure (Figure 3-2).
Maximize blowdown and restrict heat input rate to no more than 50% power at full
pressure as long as HRSG boiler water suspended solids are present, then bring the
HRSG pressure up as rapidly as silica and other boiler limitations permit.
Transition to Normal Operation:
Continue blowdown reduction in 50% increments.
Adjust phosphate chemical feed to support measured or estimated blowdown rate.
Increase tri-sodium phosphate (TSP) to increase alkalinity, add minimum levels of

di-sodium phosphate (DSP) to increase PO43 without changing pH. Mono-sodium
phosphate (MSP) should not normally be added; it is recognized that many utilities
have used MSP in the past to lower pH in conventional boilers. (Caution:) apply
MSP to reduce the alkalinity only when it has been verified that free caustic alkalinity
has, or is being delivered to the HRSG via demineralizer leakage etc.
Be precise in measuring chemical feed dose.
Monitor chemical feedpump performance.
Now is the time to conserve HRSG blowdown since excess suspended solids have
been removed, chemical feed is stable and consistent. HRSG blowdown should be
zero or close to zero during normal operation.
3-22

Hot Startup and the Impact of Hideout
Avoid making changes to boiler chemistry in reaction to chemistry change from a

HRSG trip (such as depressed or elevated pH). This chemistry change is normal
and is usually the result of hideout phenomena. Careful characterization of the
trip induced chemistry change is necessary, and it is important to avoid chasing
your tail. On the other hand, if pH elevation or depression is significant, then EPT
should be considered (see later in this section).
Up to 1 ppm excess sodium hydroxide (Figure 3-11) is considered safe and would
result in a lower probability of acidic phosphate under-deposit reactions which form
(5,6)
maricite . It could also help to neutralize any un-returned phosphate hideout. This
should be examined on a site-specific basis. And it should, however, be kept in mind
that sodium hydroxide has a relatively high liquid to vapor volatility, and caustic is a
very serious corrodent both under-deposit in the HRSG and in the turbine. It has a
fairly high distribution ratio from boiler water to steam. Thus, it is important to
monitor HRSG boiler water for free hydroxide, and steam for sodium during the
development of the optimum boiler chemistry. Free NaOH can enhance foaming in the
drum, and mechanical carryover.
3.6 OVERVIEW OF EQUILIBRIUM PHOSPHATE TREATMENT (EPT)

Although congruent phosphate treatment (sodium : phosphate molar ratio 2.2 to 2.6)
has been used successfully in a number of high pressure conventional and HRSG
boilers over the years, its use in both types of boiler has resulted in unmanageable
chemistry (phosphate hideout and return) and in some cases extensive boiler tube
damage. Symptoms include a decrease in phosphate and an increase in pH with
increasing load and, when the unit load is decreased, an increase in phosphate with pH
depression. These pH and phosphate swings are often so severe that the desired
phosphate and pH limits cannot be maintained. Attempts to maintain chemical limits
by the addition of excessive amounts of chemicals (e.g.: di-, and mono-sodium
phosphate) has resulted in acid phosphate corrosion(5,6) of boiler tubes requiring
extensive repair.
Equilibrium phosphate treatment has proven very successful in a number of high
pressure conventional boilers including some boilers which exhibited serious
phosphate hideout on congruent chemistry(7-9). The equilibrium phosphate
concentration for a specific boiler is determined by field tests described later in this
section; it is defined as the maximum concentration of phosphate which results in no
significant phosphate hideout or return without exceeding the phosphate limits for
various pressures set forth in these guidelines, Figure 3-2. The chemical limits for
normal operation on equilibrium phosphate treatment include phosphate maintained at
or near equilibrium concentration, sodium hydroxide at 0.2 to 1.0 ppm and pH
3-23

(adjusted for ammonia as described in Section 2) at 9.0 to 9.7. Equilibrium phosphate

chemistry is stable and only minor chemical adjustments are needed to operate within
these limits, while maintaining zero or close to zero blowdown. The use of chemicals is
also minimized with EPT.
Successful operation with equilibrium phosphate treatment requires accurate
monitoring of phosphate and pH (continuous instrumentation) and sodium hydroxide
(by titration). Close scrutiny of these data will ensure the desired chemical limits are
maintained around-the-clock, especially during load transition periods. This
monitoring is also critical for assessing whether the equilibrium phosphate
concentration has shifted, which can result from changes in operational procedures,
uneven flue gas temperatures, uneven heat flux patterns, deposit density, etc. A shift in
the equilibrium concentration can be determined most easily during a rapid load
decrease (e.g. normal operation, unit trip, or shutdown). It is evidenced by a sudden
increase in phosphate concentration, which may be accompanied by a significant pH
change. The correct equilibrium phosphate concentration is easily determined by
appropriate field tests, as described later.
Since the equilibrium phosphate concentration will be lower than the phosphate
concentration employed with phosphate treatment (PT), less buffering capacity will be
present to counteract the contamination. Contaminant concentration limits have been
adjusted to reflect this, and are shown on the cycle chemistry diagram for EPT (Figure
3-12). Particular emphasis should be given here to the much lower chloride boiler
water limits (Figure 3-14 compared to Figure 3-3) for EPT compared to PT.
During cold startup and other periods of excessive contamination, the phosphate
concentration should be temporarily increased to the maximum permitted for PT at the
specific HRSG pressure (Figure 3-2), as dictated by the level of contamination. During
these temporary periods of increased phosphate, sodium hydroxide should be
maintained at the normal level of 0.2 to 1.0 ppm. The unit is returned to the
equilibrium phosphate concentration as soon as the contaminant levels allow operation
without restriction on HRSG pressure.
3.7 GUIDELINES FOR EPT

Cycle chemistry target values and action levels are presented in this section for each
monitoring point for plants having HRSG drum boilers on equilibrium phosphate
treatment. A target, or normal value, and as many as four action levels are given for
each parameter at each monitoring point. This section is intended to be used by
operating staff and management personnel.
3-24

Target Values for HRSGs With Reheat on EPT

cycle chemistry diagram (Figure 3-12)
HRSG boiler water limits (it should be noted that these limits and curves are
provided for troubleshooting, commissioning, and for the monitoring campaigns
described in Section 9.5).
sodium vs. operating pressure (Figure 3-13)
chloride vs. operating pressure (Figure 3-14)
sulfate vs. operating pressure (Figure 3-15)
silica vs. operating pressure (Figure 3-16)
HRSG boiler water specific conductivity versus phosphate concentration at various

sodium to phosphate molar ratios and of phosphoric acid (Figure 3-8). (Refer to PT
Section 3.3 for information on the use of Figure 3-8.)
HRSG boiler water primary chemistry control parameters:
specific conductivity vs. pressure, at 3.0 molar ratio Na:PO4 and for boiler water
uncontaminated with chlorides and sulfates (Figure 3-17)
cation conductivity vs. pressure, at 3.0 molar ratio Na:PO4 and for boiler water
uncontaminated with chlorides and sulfates (Figure 3-18)
Copies of these figures, modified to reflect specific unit characteristics should be

included in the plant operating procedures and prominently displayed in the control
room, water and steam sample room, and the chemistry laboratory. It may be more
HRSG boiler water pH must be kept within a narrow alkaline range to maintain the
protective layer of magnetite on the internal HRSG tube surfaces. Contaminants such
as chlorides, sulfates and silica must be maintained at very low concentrations to
prevent corrosion or excessive deposits within the HRSG tubes or downstream steam
circuits.
3-25

In EPT, HRSG boiler water alkalinity is maintained with an adequate concentration of a

blend of tri-sodium phosphate and free caustic. The rationale for this treatment is
described in Section 2.
Target Values for HRSGs Without Reheat on EPT

developed for those plants that do not have reheat. While this section does not include
these values, the following will provide guidance for the determination of proper
operating values:
For the concentration values vs. pressure curves (Figures 3-13 through 3-16), the
values for concentration for non-reheat units are twice those for reheat units.
Differences between the Normal Action level for reheat and non-reheat units are
shown in Table 3-2. Values not listed in this table are identical for reheat and nonreheat units.
Table 3-2
Differences Between Normal Action Levels for Reheat and Non-Reheat Units on EPT
Sample Point
Makeup
Condensate Pump
Discharge
Parameter
Reheat
Non-Reheat
Silica, ppb
10
20
Sp. Conductivity, S/cm
0.1
0.15
with Polisher
12
without Polisher
with Polisher
0.3
0.35
without Polisher
0.2
0.25
Sodium, ppb
Condensate Polisher
Sodium, ppb
Outlet
0.2
0.25
Economizer Inlet
0.2
0.25
Saturated Steam
0.15
0.25
Sodium, ppb
Silica, ppb
10
20
Sodium, ppb
0.15
0.25
RH/Main Steam
3-26

**
Target
Sample

Oxygen, ppb
0.2
0.35
0.65
> 0.65
1-10
>15
> 20
pH, pH unitsa
9.2-9.6
< 9.2
> 9.6
W
C or S
5
< 20
>5
To -300
To +50
Parameter
Iron, ppb
With oxygen
scavenger
ORP, mV
Without oxygen
scavenger
Saturated Steam
Parameter
Target

Sample
0.15
> 0.25
0.45
> 0.45
S/cm
Sodium, ppb
>6
12
> 12
Silica, ppb
10
20
40
> 40
Target
Sample
S/cma
0.15
0.25
0.45
> 0.45
Sodium, ppb
12
> 12
Parameter
*
*
Deaerator
HP SH steam
IP SH steam
IP SH steam
LP SH steam
Chemical
feed
Chemical
feed
LP
drum
Flue gas
to stack
Chemical
feed
IP
drum
Reheater
HP
drum
HP

To steam injection
(if used)
IP
LP
Steam turbine

Target
Parameter
Sample
>1
Air inleakage,
SCFM/100 MW

Target
Sample
Parameter
Heat Recovery
Steam
Generator (HRSG)
S/cma
Condenser
Flue gas
Deaerator
pump
*
*
*
Low
pressure
(LP) section
LP
blowdown
Boiler Water
Sample
Immediate
Shutdown
Phosphated, ppm
c
c
pH, pH unitsa
<8
Sodium, ppmd
Chloride, ppb
C
T
b
b
b
b
b
b
b
b
b
b
Sililca, ppb
Parameter
Preheater
Target
Specific or cation
conductivity, S/cma
Intermediate
pressure
(IP) section
IP
blowdown
Supplemental
firing (if used)
Air Fuel
High
pressure
(HP) section
HP
blowdown
Attemperation
feed
Feedwater
pump
Chemical
feed
Combustion
Electricity
turbine and
generator
Water
Steam injection
injection
from IP steam
Bypass
Condensate
polisher
(if used)
Target
*
*
N (Normal)
Cycling
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
W = grab, weekly
N = Normal
1 = Action Level 1
2 = Action Level 2
3 = Action Level 3
a=
b=
c=
d=
Conductivity and pH measured at 25 C

See curves of maximum allowable concentration versus pressure
Must be determined
Up to 1 ppm free NaOH
Target
Sample
S/cma
0.2
> 0.2
Sodium, g/l Na
12
> 12
Parameter
10
S/cma
0.1
T or W
300

Parameter
1 (Action Level 1)
Condensate
pump

Base Load
Sample
Silica, ppb
Makeup
system
Condensate
storage

Targets
Parameter
*
*
Target
Plants with
polisher
Plants without
S/cma
polisher
Plants with
polisher
Sodium, ppb
Plants without
polisher
Sample
0.3
> 0.3
0.2
0.35
0.65
> 0.65
20
40
> 40
>6
12
> 12
T or W
200
> 200
= Core parameter
= Chemical feed
Figure 3-12
Cycle chemistry diagram for an HRSG drum unit on equilibrium phosphate treatment (plants with reheat). It should be noted that this diagram does not represent exactly any operating unit. It is only illustrative
for use in the chemistry cycle diagrams for drum type HRSG units. Operators should apply the parameters/target boxes to their actual unit. These may need customization according to Sections 1.11 and 9.5.
3-27

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
20
15
Action level 3
10
9
8
7
6
Action level 2
Action level 1
4
3
Sodium (ppm Na)
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 2700 2850
Pressure (psia)
2400
Note: Use of phosphate treatment above 2400 psia should be carefully

evaluated during commissioning
Figure 3-13
Equilibrium phosphate treatment: Boiler water sodium vs. operating pressure
(HRSG/combined cycle plants with reheat)
3-29

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
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
Action
level 2
Action
level 1
0.10
0.09
0.08
0.07
0.06
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 3-14
Equilibrium phosphate treatment: Boiler water chloride vs. operating pressure
3-30

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
3.0
2.0
1.5
1.0
0.9
0.8
0.7
0.6
0.5
Sulfate (ppm SO4)
0.4
Action
level 3
0.3
0.2
Action
level 2
Action
level 1
0.10
0.09
0.08
0.07
0.06
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 3-15
Equilibrium phosphate treatment: Boiler water sulfate vs. operating pressure
3-31

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
20
15
10
8
7
6
5
4
3
Silica (ppm SiO2)
Action
level 3
1.0
0.8
0.7
0.6
0.5
Action
level 2
0.4
Action
level 1
0.3
0.2
Normal
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 3-16
Equilibrium phosphate treatment: Boiler water silica vs. operating pressure
3-32

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
1900 2100
2300
2500
2700
130
120
110
Action level 3
100
Specific Conductivity, S/cm
90
80
70
Action level 2
60
50
40
30
Action level 1
20
Normal
10
0
600 700
900
1100
1300
1500 1700
2850
Figure 3-17
Equilibrium phosphate treatment (EPT): HRSG drum water specific conductivity
vs. operating pressure, molar ratio Na:PO4 = 3.0 (plants with reheat)
3-33

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
1900 2100
2300
2500
2700
110
100
Action level 3
90
80
70
Action level 2
60
50
40
30
Action level 1
20
Normal
10
0
600 700
900
1100
1300
1500 1700
2850
Figure 3-18
Equilibrium phosphate treatment (EPT): HRSG drum water cation conductivity vs.
operating pressure, molar ratio Na:PO4 = 3.0 (plants with reheat)
3-34

3.8 CONSIDERATIONS IN CONVERTING TO EQUILIBRIUM PHOSPHATE

TREATMENT (EPT)
The considerations involved in deciding whether to convert from the phosphate
treatment presently in use in an HRSG boiler to equilibrium phosphate treatment are
described completely in Section 9.
3.9 CONVERTING A BOILER TO EQUILIBRIUM PHOSPHATE TREATMENT

This section provides guidance on how to convert a drum HRSG to equilibrium
phosphate treatment (EPT). Specifically a road map is included to step an operator
through the various processes and procedures to develop the optimum EPT (Figure 319). As mentioned in the section on PT, these procedures can also be used for those
operators that elect to operate their drum HRSGs on PT with higher levels of phosphate
than EPT. This will help to ensure that HRSG boilers dont operate with unnecessary
hideout and return.
Step 1Review of Current PT and Chemical Clean
The review of the current phosphate treatment and the decision to chemically clean the
HRSG(10) prior to conversion to EPT are discussed in Section 9. It is noted on Figure 319, that if the problems of phosphate hideout, hideout return, corrosion of HRSG tube
walls, or failures with the current phosphate treatment, are serious for a unit in terms of
operating performance and reliability, then an operator might decide to convert to EPT
without a chemical clean. This is obviously not optimum. A utility might alternatively
consider following the previous PT guidance, which involves not chasing hideout and
not adding further acidic phosphate chemicals to the unit.
3-35

(Step 1)
Review of current PT
(Step 1)
Chemical clean and
passivation
Problems of hideout.
Corrosion and/or HRSG
tube failures are serious
(Step 2)
Unit should have no
condenser leaks and is tight
with respect to blowdown
Determine equilibrium level
Close blowdown.
Add phosphate to PT limit.
pH 9.5-9.6
(NaOH up to 1 ppm).
If return occurs, then

phosphate level is too high
Isolate PO4 feed.

Increase load.
Determine equilibrium level.
(Step 3)
Dose Only
- Tri-sodium phosphate
- NaOH (for contaminants)
- Minimize blowdown
(Step 4)
Continual check on
equilibrium level.
Normal operation.
Limits monitoring.
Look for hideout return.
Figure 3-19
Road map for converting an HRSG boiler to equilibrium phosphate
3-36

Step 2Determine Equilibrium Level

The equilibrium phosphate concentration for a particular unit should be determined by
testing the unit following its return to service after the chemical clean. Prior to
performing this test, the unit should have been operating for over a week without any
control or contaminant problems, and with the blowdown closed. This test is
performed by reducing unit load to a minimum value and keeping the blowdown
closed. The phosphate concentration is adjusted using tri-sodium phosphate only, to
near the upper limit recommended for PT (Figure 3-2), depending upon the pressure of
the HRSG circuit. The pH, corrected for ammonia (Section 2), should be adjusted to
9.59.6 with sodium hydroxide, as required, to ensure the presence of a small amount
of free sodium hydroxide, but less than 1 ppm as NaOH. At this stage, the phosphate
and sodium hydroxide feeds are discontinued and the unit is ramped to full load.
Over the next several hours, the phosphate concentration will be reduced in the HRSG
boiler drum via the hideout mechanism, finally reaching a minimum plateau level,
which is the equilibrium phosphate concentration. This then becomes the target
phosphate concentration for the unit during normal operation. Carrying phosphate
levels above this concentration will result in unnecessary hideout and hideout return.
Step 3Normal Operation
Once the initial equilibrium phosphate level has been determined for the HRSG, then
the unique operating limits for the unit should be determined. The cycle chemistry
diagrams and contaminant curves, that are provided in Figure 3-8 and Figures 3-12 to
3-16 in this section, should be regarded purely as a guide, and need to be customized
for each unit or HRSG circuit. The importance of this customization cannot be
overemphasized: it is very important to measure the carryover from the HRSG drum
into the steam for each unit and to use this information to develop specific unit
operating chemical guidelines. It is of particular concern with EPT, operating with a
very small level of free hydroxide, that strict attention is paid to the steam sodium
levels.
During normal operation, only tri-sodium phosphate should be added to the HRSG
boiler water. Sodium hydroxide can be added for contaminant control as discussed
later in this section. The use of the blowdown should be minimized, which will
minimize the addition of chemicals to the unit.
Step 4Continual Check of Phosphate Level
The HRSG boiler water should be continuously monitored during normal operation for
pH and phosphate, and particularly during periods of rapid load reduction. The use of
specific or cation conductivity measurements provide an indirect indication of
3-37

phosphate as previously described (see Figures 3-8, 3-17 and 3-18), and may be more
convenient to monitor than phosphate. Since the chemical requirements of a unit can
change over time, significant shifts of the equilibrium phosphate concentration can and
do occur. If the required load changes needed to make these observations do not occur
during the course of normal operations, the unit should be operated as required at
three to six month intervals to obtain the necessary data and to make any needed
changes in the equilibrium phosphate limit.
If during a load reduction or a shutdown, hideout return is observed, then this should
be a strong indication that the unit has not been operating at its equilibrium phosphate
level. In this case, the utility should re-determine the equilibrium level by following
the steps delineated under Step 2, Determine Equilibrium Level, Figure 3-19.
It is also important during these periodic checks to ensure that the sodium levels in the
HRSG boiler water are consistent with the pressure/concentration curves for sodium,
Figure 3-13, to prevent possible damage to the turbine from mechanical and vaporous
carryover of sodium compounds. The free NaOH should be restricted to a range of 0.2
to 1.0 ppm, again being consistent with Figure 3-13.
3.10 OPERATION DURING UPSET CONDITIONS WITH EPT

The following discussion is concerned with EPT during non-normal conditions;
specifically, what modifications to EPT are necessary during these contamination
episodes and how should an operator react?
When contamination occurs as indicated by conductivity, the blowdown should be
opened and the source of contamination isolated quickly to minimize chemical upset.
The concentrations of chloride and sulfate in the boiler can be determined using an ion
chromatograph if available. If the concentrations exceed limits (such as those given in
Figures 3-14 and 3-15) the pressure of the unit should be dropped to stay within the
sliding chloride and sulfate pressure limits adopted for the plant. In order to provide
chemical protection during high contamination episodes, the phosphate concentration
can be increased to the limit specified in the guidelines for PT (Figure 3-2). Using
sodium hydroxide, the pH should be maintained within the normal limits of 9.1 to 9.6
adjusted for the presence of ammonia. Mono-sodium phosphate can be used for the
severest emergencies only; it should not be used during normal operations because of
the added risk of HRSG boiler tube failure. If at any time the HRSG blowdown pH
falls to below 8, consideration should be given to taking the unit off line, draining, and
assessing the need for chemical cleaning. After the source of contamination has been
isolated and the concentration of the contaminants in the blowdown are within limits,
the unit can be converted back to equilibrium chemistry.
3-38

3.11 UNIT STARTUP AND SHUTDOWN

Cold Startup
In order to give added protection against contaminant ingress during the initial stages
of operation, the phosphate concentration may be adjusted to the maximum
concentration permitted by the guidelines for PT (Figure 3-2). The pH should be
maintained at 9.1 to 9.6, adjusted for ammonia. During startup, this adjustment will
likely be significant if the use of excessive reducing agent is necessitated by high
feedwater oxygen levels. Failure to account for positive bias of the pH due to the
presence of ammonia will lead to an actual boiler pH below the recommended limits
and the possible subsequent formation of acidic species of phosphate. The unit should
be converted to equilibrium chemistry when the contamination levels are at or below
the pressure/contaminant curves (Figures 3-14 to 3-18). Heavy blowdown can be
maintained throughout the startup until contaminant levels are well within limits at
which time the blowdown should be isolated. The blowdown remains isolated during
normal operation except in periods of abnormal contamination.
Unit Trip With Normal Contaminant Concentrations

Phosphate concentration (or conductivity as an indirect indication) and pH should be
monitored closely when a unit trips. A sudden release of phosphate (phosphate
hideout return) indicates that the phosphate concentration target used in normal
operation is higher than the true equilibrium level and therefore requires adjustment.
If the release of phosphate is accompanied by a pH swing, this characterizes the
phosphate hideout species as either acidic or basic. If the pH change is significant, the
pH and phosphate during normal operation should be monitored closely around the
clock to determine where the chemical limits are being exceeded and chemical control
adjustments made accordingly. As indicated previously, the equilibrium level should
also be redetermined.
Unit Shutdown
During shutdown, the pH and phosphate are monitored closely to determine whether
the normal equilibrium chemical limits are correct and are being maintained around
the clock as detailed above. During the shutdown process, if the pH drops below the
bottom limit (Figure 3-11) sodium hydroxide can be added to drive the pH within the
acceptable range to protect the HRSG.
3-39

3.12 REFERENCES
1. Cycle Chemistry Guidelines for Fossil Plants: Phosphate Treatment for Drum Units.
Electric Power Research Institute, Palo Alto, Calif., EPRI TR-103665, December 1994.
2. W. Bosselmann and R. Brunner, Conductivity of Phosphate Solutions.
Kraftwerkstechnik, 58, February 1979, pp. 175-178.
3. Membrane Filtration Comparison Charts (Magnetite), Copyright Babcock & Wilcox
Company 1964, 1970 Available from Babcock & Wilcox Company, Barberton, Ohio
44203.
4. L. O. Brestel, Boiler Start-Up and Shut-Down Chemistry Control, 13th Electric
Utility Chemistry Workshop, University of Illinois at Urbana-Champaign, Illinois,
March 16-18, 1993.
5. R. B. Dooley and S. Paterson, Phosphate Treatment: Boiler Tube Failures Lead to
Optimum Treatment, IWC Paper-94-50, International Water Conference,
Pittsburgh, Pa., October 31/November 2, 1994.
6. R. B. Dooley and W. P. McNaughton, Boiler Tube Failures Theory and Practice, Vols. 1,
2, and 3, EPRI TR-105261, June 1996.
7. J. Stodola, Review of Boiler Water Alkalinity Control, in Proceedings of the
International Water Conference, October 1986, pp. 234-242.
8. D. D. Goldstrohm and T. W. Robertson, Low Phosphate-Low Sodium Hydroxide
Treatment in 2600 psig Boilers at Salt River Projects Coronado Station, in
Proceedings of the International Water Conference, October 1989, pp. 493-499.
9. J. Stodola, Rationale for Equilibrium Phosphate Treatment, in Proceedings of
International Conference on Fossil Plant Cycle Chemistry, Electric Power Research
Institute, Palo Alto, Calif., TR-100195, December 1991, p. 1-41.
10. Guidelines for Chemical Cleaning of Fossil-Fueled Steam Generation Equipment,
Electric Power Research Institute, Palo Alto, Calif., TR-102401, June 1993.
3-40
4
CYCLES WITH DRUM HRSGs ON ALL-VOLATILE
TREATMENT (AVT)
4.1 INTRODUCTION TO ALL-VOLATILE TREATMENT

An overview of the all-volatile treatment (AVT) philosophy for drum HRSGs was given
in Section 2. This Section provides cycle chemistry target values and action levels for
each monitoring point for combined cycle plants having HRSG drum boilers on AVT.
This section is intended to be used by operating staff and management personnel.
To determine whether a particular HRSG drum cycle should be operated on AVT, the
reader is first referenced to Section 9, and advised to follow the HRSG Boiler Water
Selection procedure outlined in the road map (Figure 9-5).
of cycles presently available and under development, it is not possible to include each
in these guidelines. The cycle diagram chosen (Figure 4-1) for the presentation of target
values and action levels for drum units is the same as that used in Section 3 for drum
units on PT or EPT. In AVT, only volatile chemicals are used, most commonly
ammonia and a reducing agent such as hydrazine.
This cycle diagram is one of the more complex available, having three drums, each
operating at a different pressure (low, intermediate and high). Only the reheat cycle is
included; however, guidance for establishing limits for non-reheat units is given in
subsequent parts of this section. Reheat and superheated (main) steam chemistry target
values in the EPRI report Cycle Chemistry Guidelines for Fossil Plants: All-Volatile
Treatment(1) were found to adequately protect the steam turbine and the rest of the heat
cycle from corrosion or deposition. In recognition of this fact, AVT limits were set for
reheat and superheat steam in this document for AVT treated units.
The principles established in this section should serve as guidelines regardless of the
cycle diagram configuration for which chemistry target values are to be established.
For example, some cycles will not have preheaters or deaerators. Suitable adjustments
must be made when establishing target values for these cases (see Section 1.11).
4-1

Cycles with Drum HRSGs on All-Volatile Treatment (AVT)
Also, in some cycles, the low and/or intermediate pressure superheat steam may not be
utilized in the steam turbine, but is instead used for cogeneration, NO x control or for
some other purpose. In such cases, the target values for this steam must be established
to meet the requirements of the intended end use, whatever that might be.
4.2 USE OF REDUCING AGENTS (OXYGEN SCAVENGERS)

As previously discussed, the use of hydrazine or other oxygen scavengers has been
found to be unnecessary by several investigators(2) when all-ferrous metallurgy is
provided, such as commonly the case with combustion turbine/combined cycles.
The use of reducing agents such as hydrazine should be carefully considered,
especially when used in conjunction with AVT, particularly in the LP cycle. Hydrazine
will concentrate in the LP cycle and can lead to flow-accelerated corrosion at tube
(3)
bends in the LP HRSG cycle . Such failures have become common, and are discussed
in Section 1.10. The whole area of optimizing the feedwater treatment, including the
use of reducing agents, is discussed in Section 9.3.
4.3 GUIDELINES FOR AVT

Target values and action levels for all key cycle contaminants for HRSG drum boilers
on AVT are presented as a continuum over a broad range of operating pressures in
Figures 4-2 through 4-6. As mentioned in Sections 2 and 3, cycle contaminant values
for the minimum HRSG boiler pressure of 600 psi (4.1 MPa) depicted on these curves
should be used for all boilers operating at 600 psi (4.1 MPa) and below. This is based
on the rationale that:
There is considerable uncertainty in values extrapolated from the ray diagram

(Figure 2-6) at pressure below 600 psi (4.1 MPa).
The contaminant values at 600 psi (4.1 Mpa) provide conservatism for boilers
operating at 600 psi (4.1 MPa) and below.
4.4 AVT GUIDANCE

Cycle chemistry target values and action levels are presented in this section for each
monitoring point for plants having HRSG drum boilers on all-volatile treatment. A
target, or normal value, and as many as four action levels are given for each parameter
at each monitoring point. This section is intended to be used by operating staff and
management personnel.
4-2

Similarly designed HRSGs may behave differently in response to additive chemicals,

impurity ingress, and feedwater corrosion product ingress because of interaction with
the transport of contaminants from pre-HRSG systems having differences in balance-ofplant designs and materials choices, differences in make-up system designs and
operation, variable effectiveness of air-removal equipment and variable avoidance of
cooling water in-leakage control.
Research has shown that the concentration of impurities within the interstices of
deposits formed on evaporator tube surfaces (iron oxides, nickel and zinc oxides, and
copper etc.) can result in the breakdown of the protective magnetite and lead to
under-deposit tube metal damage, especially by the hydrogen damage mechanism.
When such contamination occurs it will require that the chemist/operator modify the
chemical dosage to avoid localized concentration. In the long term, the accumulated
deposits should be removed by timely chemical cleaning to avoid HRSG tube
damage and failures. Retarding the formation of such deposits is one of the reasons for
employing oxygenated treatment (OT) as discussed in Section 7. The philosophy of
operating with an oxidizing feedwater is discussed in Section 9. This has been very
successfully employed in conventional fossil plants(4).
Here it is suggested that the road map approach described later in this section should
be followed to optimize the HRSG boilers and feedwaters AVT for all possible
operating circumstances. Reference should also be made to Section 9.
4.5 TARGET VALUES FOR PLANTS WITH REHEAT ON AVT

HRSG boiler water limits (it should be noted that the limits and curves for sodium,
chloride, sulfate and silica are provided for troubleshooting, commissioning and for
the monitoring campaigns described in Section 9.5)
sodium versus operating pressure (Figure 4-2)
chloride versus operating pressure (Figure 4-3)
sulfate versus operating pressure (Figure 4-4)
silica versus operating pressure (Figure 4-5)
HRSG boiler water primary control parameter:

4-3

cation conductivity versus operating pressure (Figure 4-6)
Copies of Figures 4-1 through 4-6, modified if necessary to reflect specific unit
characteristics and/or experience, could be included in the plant operating procedures
and prominently displayed in the control room, water and steam sample room, and
chemistry laboratory. It may be more convenient to develop a separate figure, based on
Figure 4-1, which only includes the core parameters for the specific HRSG unit.
4-4

Cycles with Drum HRSGs on All-Volatile Treatment (AVT)EPRI Licensed Material

Target
Sample
0.2
0.35
0.65
> 0.65
Oxygen, ppb (switchable with CPD)
Iron, ppb
> 15
< 9.2
> 9.6
>5
1-10
9.2-9.6
> 20
pH, pH unitsa
C or S
< 20
To -300
To +50
Parameter
*
*

With oxygen
scavenger
Without
oxygen
scavenger
ORP, mV
Saturated Steam
Target

Sample
S/cma
0.15
> 0.25
0.45
> 0.45
Sodium, ppb
12
> 12
Silica
10
20
40
> 40
Parameter
Target
Parameter
*
*
Deaerator
Sample
Sodium, ppb
12
> 12
S/cma
0.15
0.25
0.45
> 0.45
HP SH steam
IP SH steam
IP SH steam
LP SH steam
Chemical
feed
Chemical
feed
LP
drum
Flue gas
to stack
Chemical
feed
IP
drum
Reheater
HP
drum
HP

To steam injection
(if used)

Target
Parameter
Sample
>1
Air inleakage,
scfm/100 MW
IP
LP
Steam turbine

Target
Parameter
Heat Recovery
Steam
Generator (HRSG)
Sample
S/cma
Condenser
Flue gas
Preheater
Deaerator
pump
LP
blowdown
Boiler Water
Parameter
*
*
Target
Cation conductivity, S/cm
Low
pressure
(LP) section
Sample
Immediate
Shutdown
pH, pH, unitsa
<8
Sodium, ppb
Chloride, ppb
Silica, ppb
Intermediate
pressure
(IP) section
IP
blowdown
HP
blowdown
Supplemental
firing (if used)
Air Fuel
High
pressure
(HP) section
Attemperation
feed
Feedwater
pump
Chemical
feed
Target
Combustion
Electricity
turbine and
generator
Water
Steam injection
injection
from IP steam
Bypass
Condensate
polisher
(if used)
*
*
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
Target Values
C
S
D
W
T
N = Normal
1 = Action Level 1
2 = Action Level 2
3 = Action Level 3
= continuous
= grab, once per shift
= grab, once per day
= grab, once per week
= troubleshooting and commissioning
a=
b=
c=
d=

Must be determined
See curves of allowable cation conductivity vs. pressure
Target
Sample
S/cma
0.2
> 0.2
Sodium, ppb
12
> 12
Parameter
Footnotes
10
S/cma
0.1
T or W
300

N (Normal)
Condensate
pump
Parameter
Base Load
Sample
Silica, ppb
Makeup
system
Condensate
storage

Targets
Parameter
*
*
S/cma
Target
Plants with
polisher
Plants without
polisher
Oxygen, ppb,
(switchable with EI)
Sodium, ppb
Plants with
polisher
Plants without
polisher
Sample
0.3
> 0.3
0.2
0.35
0.65
20
40
> 40
>6
> 0.65
12
> 12
T or W
200
> 200
= Core parameter
= Chemical feed
Figure 4-1
Cycle Chemistry Diagram for a HRSG Drum Unit on All-Volatile Treatment (Plants With Reheat). It should be noted that this diagram does not represent exactly any operating unit. It is only illustrative for use in
the chemistry cycle diagrams for drum type HRSG units. Operators should apply the parameters/target boxes to their actual unit. These may need customization according to Sections 1.11 and 9.5.
4-5

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
1700
1900
2100
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
600 700
900
1100
1300
1500
Pressure (psia)
Figure 4-2
All-Volatile Treatment: HRSG Drum Boiler Water Sodium vs. Operating Pressure
4-7

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
2300
2500
2700 2850
3.0
2.0
1.5
1.0
0.9
0.8
0.7
0.6
Action level 3
0.5
0.4
Action
level 2
Chloride (ppm Cl)
0.3
0.2
Action
level 1
0.10
0.09
0.08
0.07
0.06
Normal
0.05
0.04
0.03
0.02
0.01
600 700
900
1100
1300
1500 1700 1900

Pressure (psia)
2100
Figure 4-3
All-Volatile Treatment: HRSG Drum Boiler Water Chloride vs. Operating Pressure
4-8

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
3.0
2.0
1.5
1.0
0.9
0.8
0.7
0.6
Action level 3
0.5
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
Figure 4-4
All-Volatile Treatment: HRSG Drum Boiler Water Sulfate vs. Operating Pressure
4-9

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
Action
level 1
Normal
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 4-5
All-Volatile Treatment: HRSG Drum Boiler Water Silica vs. Operating Pressure
4-10

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
2500
2700 2850
200
100
90
80
70
60
50
40
Action level 3
30
Cation Conductivity - S/cm
20
Action
level 2
Action
level 1
10
9
8
7
6
Normal
5
4
3
1
600 700
900
1100
1300
1500 1700 1900 2100

2300
Figure 4-6
All-Volatile Treatment: HRSG Drum Boiler Water Cation Conductivity vs. Operating
Pressure (HRSG/Combined Cycle Plants With Reheat)
4-11

4.6 TARGET VALUES FOR PLANTS WITHOUT REHEAT

The sample points, monitoring parameters, target values, and action levels have also
been established for those plants that do not have reheat. While this section does not
include separate cycle diagrams with these values, the following will provide guidance
for the determination of proper operating values:
For the concentration and cation conductivity vs. pressure curves (Figures 4-2
through 4-6), the values for concentration and cation conductivity for non-reheat
units are twice those for reheat units.
Differences between the Normal Action Level for reheat and non-reheat units are
shown in Table 4-1. Values not listed in this table are the same for reheat and nonreheat units.
Table 4-1
Differences Between Normal Action Levels for Reheat and Non-Reheat Units on AVT
Sample Point
Reheat
Non-Reheat
with Polisher
12
without Polisher
with Polisher
0.3
0.35
without Polisher
0.2
0.25
0.2
0.25
Economizer Inlet
0.2
0.25
Saturated Steam
Sodium, ppb
0.15
0.25
Silica, ppb
10
20
Sodium, ppb
0.15
0.25
Condensate Pump
Discharge
Parameter
Sodium, ppb
Polisher Outlet
Sodium, ppb

RH/Main Steam
4-12

4.7 CONVERTING A HRSG DRUM BOILER CYCLE TO AVT OR OPTIMIZING

THE CURRENT AVT
A road map is presented in Figure 4-7 to assist the user in converting a HRSG drum
boiler cycle from another treatment system (maybe phosphate) to AVT, or in
optimizing the current AVT. This road map and the procedures may be followed after
the selection process in Section 9 has indicated that AVT is a suitable chemistry for a
particular HRSG circuit. Following is an explanation of the various steps in the
process:
Step 1Review Current Treatment
Here the first part of this step is to determine if the unit is suitable for conversion to
AVT. This can be performed by answering some of the following questions:
Historically has the feedwater cation conductivity most often been below 0.2
S/cm? This might indicate that condenser leakage over a period of time has not
been of concern.
Can the HRSG boiler meet the cation conductivity requirements (Figure 4-6)?
Does the unit have a condensate polisher?
Does the unit have a satisfactory monitoring system having the ability to monitor
the essential core parameters as indicated in Figure 4-1?
If the answers to these questions are positive, then the unit may be suitable for
conversion to AVT.
The second part of this step will be accomplished by a complete review of the current
and past experience with the current treatment system (phosphate or AVT). In many
cases, the operating experience will be good, and indicate that no chemical control
problems have been experienced, that no HRSG evaporator tube failures relating to
waterside problems have occurred in the last five years, that no turbine deposition or
blade failure problems have occurred, and that the feedwater is operating in the
optimum fashion with minimum levels of feedwater corrosion products. In such cases
of good experience, no changes need to be made. However, it is suggested that the
road map be reviewed as there may be considerable economic savings to be gained.
In other cases, some problems may have occurred or still be occurring, which
necessitate a more thorough review and optimization. Information is provided in this
step for units with HRSGs currently operating on phosphate treatment and for units
operating on AVT.
4-13

For Units with HRSGs Currently Operating with Phosphate Treatment. The initial review
involves operating experience with the current phosphate treatment and particularly
determining whether phosphate hideout and return occurs, and whether excessive
sodium phosphate carryover occurs(5).
Do phosphate hideout and return still occur, together with pH instability during
transients, shutdown and startup?
Another question is has the boiler experienced any HRSG tube failures in the last five
years, and have any of these been waterside related?. Here the relevant failure
mechanisms are hydrogen damage, caustic gouging, acid phosphate corrosion, or
(6)
corrosion fatigue . The last is important for AVT units as well, as it has been shown
that pH depressions, which can occur during shutdown, load reductions, and continue
into the early startup period can exacerbate the corrosion fatigue process. Corrosion
fatigue in HRSGs was discussed in Section 1. A very convenient way of determining
whether the HRSG water chemistry may influence corrosion fatigue is to follow the
process in the latest EPRI Corrosion Fatigue Reports and particularly the influence
diagram included in Volume 4(7).
Another question is whether any deposits have been observed in the turbine.
A review of condenser in-leakage and any makeup water contaminant excursions
should also be made.
If the answer to any or some of these questions is positive, implying that the current
phosphate treatment is not providing adequate chemical control, then it is suggested
that the other road map steps in Figure 4-7 should be followed.
For Units Currently Operating on AVT. There are a large number of HRSG drum units
already operating on AVT. However, it is advisable to review the operating experience

to-date and to answer the following questions; the AVT may be set up incorrectly.
Has the unit experienced any of the problems relating to the generation, transport
and deposition of feedwater corrosion products?
Does the HRSG boiler water experience pH depressions during the shutdown and
early startup periods which require the addition of either phosphate or caustic?
Are chemicals other than tri-sodium phosphate or sodium hydroxide added to the
HRSG boiler drum?
Does the feedwater cation conductivity often and significantly rise above 0.2
S/cm?
4-14

The questions on HRSG tube failures, turbine problems and condenser and makeup
water contaminants in the section above for units on phosphate treatment are also
applicable here.
AVT is not providing optimum chemical control, then it is suggested that the other
road map steps of Figure 4-7 should be followed.
Operating problems due to

feedwater chemistry?
Review current
treatment
(Step 1)
(Step 2)
Determine suitablilty
of unit for AVT;
condensate polisher?
Core instruments?
To determine optimum
feedwater
Baseline
monitoring
(Step 3)
Representative conditions
with and without oxygen
scavenger
(Step 4)
Boiler chemical
clean
(Step 5)
Develop unit specific AVT

guidelines (measure
mechanical carryover etc)
To minimize feedwater
corrosion products
(Step 9)
(Step 6)
Monitoring to compare
with baseline
Not satisfactory. Not

able to meet limits
(Step 8)
(Step 7)
Normal operation
Continual check of
chemistry
Figure 4-7
Road Map to Convert a HRSG Drum Boiler Cycle with All-Ferrous Feedwater to
AVT and/or Develop the Optimum AVT.
4-15

Step 2Base-Line Monitoring on Current Chemistry

If the review in Step 1 indicates that the unit is suitable for conversion to AVT or that
the current AVT requires optimizing, then Step 2 involves a complete base-line
monitoring program to quantify the chemical parameters for the particular unit in
question and in Step 3 to determine the optimum feedwater treatment. This program
would utilize the installed core chemistry monitoring system, supplemented by the
other parameters in the cycle chemistry diagram (Figure 4-1).
The monitoring program should pay particular attention to the adequacy of the
makeup and chemical feed systems, condenser tightness, air ingress, and corrosion
product transport.
This monitoring involves taking a thumb-print of the unit under typical operating
conditions to identify under controlled conditions exactly how the unit chemistry is
behaving. It may involve a review of the operating chemistry logs, but this often is not
satisfactory and it is preferable to adopt a monitoring campaign. Before this campaign
is initiated, it is important to review the chemistry monitoring capability and
reliability(8).
The monitoring campaign should include:
Varying Operating Conditionsbase-load, startup, shutdown, overpressure, etc.
HRSG Boiler Water Chemistry with Blowdown Open and Closedsodium,

phosphate, free hydroxide, chloride, sulfate, silica, pH, cation conductivity, etc.
Steam Chemistrycation conductivity, sodium, phosphate, free sodium hydroxide,

chloride, silica, sulfate, etc.
Feedwater Chemistrycation conductivity, specific conductivity, corrosion

products (Fe, Cu if included in cycle), oxygen, pH, oxidizing-reducing potential
(ORP), etc.
Operation of Condensate Polishers (if employed)
Mechanical carryover (moisture) and chemical volatility in the steam must be measured
by monitoring total carryover (Section 2). Concern must also be given to any
contaminants that may be contributed to the steam by feedwater utilized for steam
temperature control (attemperation).
For the feedwater, there is a need to review the hydrazine (or alternatives)
concentration. For all-ferrous feedwater systems common to HRSG cycles, the
feedwater should be monitored with and without hydrazine additives or alternatives.
4-16

It should be noted that the lower the oxygen (<< 5 ppb) and the higher the hydrazine
(>> 20 ppb), the more reducing is the feedwater and the more feedwater corrosion
products (iron) that will be generated and flow into the HRSG. This has the potential to
make the HRSG dirtier, and to require chemical cleaning sooner. As noted previously,
the use of hydrazine or hydrazine substitutes may appreciably increase the likelihood
of FAC with AVT, particularly in the LP HRSG circuit (Section 1).
The outcome from this step should be a quantification of those problems recognized in
Step 1.
Step 3Evaluate Reducing Agent (Oxygen Scavenger) Requirements
The next step, which is really a subset of Step 2, involves a series of tests to minimize
the generation and transport of feedwater corrosion products. This is also discussed in
Section 9.
In conventional plants, many utilities with the all-ferrous systems common on HRSG
cycles have found that, with proper air in-leakage control, a reducing agent (hydrazine)
can be eliminated without jeopardizing chemistry control on the unit(2).
In Step 3, a series of tests should be performed to evaluate the need for oxygen
scavenging and, if needed, to determine the proper scavenger levels. The test should
utilize the monitoring system instrumentation (used in Step 2) while varying hydrazine
dosage. Particular note should be made of dissolved oxygen levels and the level of
corrosion products generated during each test run.
Particular note should also be made of the fact that there can be a long lag time
(months) between changes in feedwater chemistry and corrosion product transport, so
careful planning is needed for accurate, extended tests.
Step 4Evaluation of Need for Chemical Cleaning HRSG Boiler
Once the base-line monitoring (Step 2) has been completed and the optimum feedwater
treatment has been determined, the HRSG boiler should be chemically cleaned prior to
converting to the new AVT. If this isnt performed when converting from phosphate
treatment, then the unit may experience high and/or varying cation conductivities and
phosphate levels after conversion. Cation conductivity control (Figure 4-6) will become
more critical in dirty HRSG boilers.
Step 5Development of Unit Specific AVT Guidelines
The importance of this step cant be overemphasized as survey results from
conventional unit users have indicated that the development of unit specific guidelines
4-17

is performed very infrequently. Most utilities just use the appropriate published
guideline target values and action levels and do not customize the guidance into
specific unit cycle chemistry guidelines.
The results of this step should be unique normal target and action levels for the specific
unit.
The guidelines represented on the cycle chemistry diagrams (Figure 4-1) are based
upon representative mechanical carryover and the distribution ratios (ray diagram) for
common boiler water contaminants, as described in Section 2. It is imperative that the
actual mechanical carryover rates determined by testing in Step 2 be used.
Determination of carryover is usually accomplished by measurement of sodium in the
saturated steam exiting the boiler drum. For HRSG boilers on AVT, it is practically
impossible to measure carryover using the sodium trace technique without
additional sodium present in the boiler water. Sodium phosphate (Na 3PO4) could be
added to stay within the requirement for less than 1 ppm sodium under AVT. This
would allow moisture carryover measurements to 0.1% (1 ppb Na). Based upon the
test results, the guidelines can be customized for a specific unit. The detailed
procedure is outlined in Section 2 of this document.
An operator should also look carefully at the boiler water cation conductivity limits and
develop a set of customized control limits for each HRSG boiler. Figure 4-6 provides
consensus guidance based on possible boiler water contaminants as described in
Section 2. The monitoring Step 2 should have provided information on HRSG boiler
water cation conductivity as a function of operating with the blowdown open and
closed. If the HRSG boiler water cation conductivity is excessive, then there is a clear
need to determine what is causing it, and whether it could be harmful.
A series of tests can be performed with the blowdown closed, while monitoring the
steam parameters (cation conductivity, chloride, sulfate, sodium) as a function of the
boiler water cation conductivity to reach an optimum boiler water limit.
Step 5 may have to be repeated based on the unit not being able to meet the developed
limits (Step 9).
Steps 6, 7, 8 and 9Adjustments Based on Continual Monitoring
In these steps monitoring continues in order to compare chemistry parameters with the
customized guidelines established in Step 5. Depending upon results, certain
adjustments may be required to further customize the guidelines. Through an iteration
of these steps, a realistic set of guidelines is established which will minimize corrosion
and optimize operations.
4-18

Step 6 is also a very important step and links with Step 5. It is essentially a repeat of
Step 2. The same matrix of operating conditions and parameters should be reviewed.
Steps 5 and 6 should be performed in an iterative fashion as needed to fully optimize
the HRSGs AVT.
Under Step 7, Normal Operation, the unit or individual HRSG circuit should be
operating with optimum all-volatile treatment. This should involve minimum
feedwater corrosion products entering the HRSG at the economizer inlet, the oxygen
scavenger should have been minimized and perhaps eliminated for the all-ferrous
systems common in HRSG cycles. The oxygen level should be above 1 ppb at the
economizer inlet. There should be no cases where chemical/operating personnel add
the wrong chemicals and they should know exactly what to do in the case of a
contaminant ingress. This is outlined later in this section.
Contaminant episodes need to be dealt with promptly. The source of contamination
needs to be removed as soon as possible, pressure restrictions applied if maximum
contaminant levels are exceeded and boiler water chemistry adjusted as needed to get
back into the control limits established for the unit.
There should be at least a minimum level of instrumentation on the unit (as indicated
by the core parameters in Figure 4-1), and the key monitoring points and parameters
should be alarmed in the control room.
4.8 NORMAL OPERATION FOR HRSG DRUM UNITS ON AVT

As noted previously, monitoring of cycle water chemistry is particularly important for
HRSG drum units on AVT. This is primarily due to the fact that there is practically no
buffering capacity in the boiler water to protect the unit from impurity ingress.
Minimization of air in-leakage is also critical, especially when oxygen scavenging is
minimized or eliminated. Air in-leakage also introduces carbon dioxide into the cycle
which may promote corrosion and also rapidly depletes the anion resin capacity of the
condensate polishers, if used.
Condensate polishing, while possibly not essential for units with titanium tubed
condensers, is very desirable in maintaining proper cycle chemistry. Polishing is
considered essential for units on sea water or high solids cooling tower water for
condenser cooling.
Cation conductivity of the HRSG boiler water should be monitored as a reliable, and
primary method to determine the onset of contaminant ingress (Figure 4-6).
4-19

suspended oxide in the boiler water.
The makeup treatment system may require review and enhancements for units
contemplating AVT operation.
4.9 REACTION TO CONTAMINANTS IN THE CYCLE

Condenser cooling water in-leakage or makeup water contamination can and will occur
in an HRSG cycle. The reaction to these is dependent on the kind of contamination.
Three examples could be:
chloride or sulfate excursions due to condenser in-leakage,
caustic or acid contamination from makeup (or condensate polisher if utilized)

regenerant, or
silica from extraneous sources.
Also in some combined cycle units there is a question of condensate returns which may
be contaminated.
The entrance of chloride or sulfate to the cycle will be immediately detected by an
increase of boiler water cation conductivity. (This will not be true for caustic or silica
contamination.) Chlorides and sulfates may cause a depression in boiler water pH,
with disastrous results if not quickly corrected. For small leakages, increased
blowdown may suffice. Generally, however, buffering chemicals will need to be added
to the HRSG boiler. Small amounts of caustic or tri-sodium phosphate (up to 1 ppm
free hydroxide) can be added at this point, but caution has to be taken that excessive
concentrations are not allowed to occur and possibly produce undesirable results, such
as caustic gouging in the boiler, or carryover into the steam. The safest procedure is to
convert to equilibrium phosphate chemistry (only tri-sodium phosphate additions)
during these periods, as described in Section 3. In either case it is important to monitor
the steam chemistry for sodium and ensure that the levels stay within the normal
limits. Some relief may also be gained by dropping pressure on the unit. The last
resort would be to take the unit off line if the pH is below 8 and still decreasing.
Silica ingress can be controlled by increased blowdown and/or reducing unit pressure.
Caustic ingress can be similarly controlled, if levels are low. High caustic may
necessitate tripping the unit, as the addition of phosphoric acid or acid phosphates for
caustic neutralization are considered to be a dangerous practice.
4-20

4.10 STARTUP AND SHUTDOWN OPERATION

Unit startup is facilitated greatly if condensate polishing is available, through the
installation and use of a feedwater cleanup loop (recirculation of feedwater to the
condenser).
Some units may experience a HRSG boiler pH depression during shutdown. During
the startup, it is important to identify whether this is due to a decrease of ammonia
(because of the increasing distribution ratio) or to contaminant ingress (carbon dioxide
or dissolved acids).
When the boiler water pH is depressed by acid contaminants, units can be started on
phosphate chemistry, Section 3 (only tri-sodium phosphate additions) or with small (<
1 ppm) additions of NaOH before gradually converting over to AVT. This period of
adjustment permits the operating staff to ensure, by chemistry monitoring, that
conditions are suitable for the establishment of AVT. The important overriding
philosophy here is that adjusting chemicals (phosphate or caustic) do not necessarily
have to be automatically added to the boiler on every startup. Maximum use of
blowdown may be required during startup to minimize boiler contaminants. If the
carefully controlled addition of phosphate or caustic is necessary for some time, which
extends into the period where the unit is operating at full- (or over-) pressure, then
special care should be taken that excessive carryover into the steam does not occur.
Operation at reduced boiler pressures may be preferable until cycle chemistry is under
control.
For shutdowns of anticipated short durations, the chemistry can be adjusted with
ammonia and hydrazine (if used). Again the preferred practice is not to add any
chemicals but to shut down with the optimum operating chemistry. The unit should be
bottled up under a nitrogen cap. Performed properly, this will minimize air intrusion
effects, including pH depression by carbon dioxide. As indicated above, a pH
depression can also occur during shutdown for AVT units, probably because ammonia
dissipates by volatilization.
Longer shutdown periods are accomplished by one of two methods:
a wet layup with a pH of 10.0 achieved with ammonia, and up to 200 ppm of
hydrazine, and condensate-quality water plus a pressurized nitrogen blanket; or
a dry layup in which a boiler is drained hot and purged with nitrogen or
dehumidified air.
Additional guidance for layup can be found in Section 10.
4-21

4.11 CYCLING AND PEAKING OPERATION

Tight control of water chemistry is especially important for units operated in a cycling
mode because of the potential for increased corrosion and contaminant ingress during
the frequent startups inherent in this type of operation.
Problems during cycling and peaking include the introduction of increased oxygen and
silica to the cycle, high levels of iron, increased startup times, material stresses, and
HRSG and turbine deposits and corrosion.
Oxygen and carbon dioxide control are of supreme importance with cycling and
peaking operation. High oxygen and carbon dioxide levels may lead to increased
corrosion, manifested by high iron values. To mitigate this corrosive effect, the
dissolved oxygen in the feedwater (economizer inlet) and HRSG boiler water during
startup and before firing should be less than 100 ppb, and the iron in the feedwater
should be less than 100 ppb. Plants with air-cooled condensers may have difficulty
reaching this limit.
In conventional fossil plants, oxygen and carbon dioxide can be controlled by one or
more of the following measures:
makeup water deaeration
protecting condensate storage tanks from air by:
floating covers
diaphragms
nitrogen purges
maintaining condenser vacuum during shutdowns
hotwell sparging
installing a deaerator in the heat cycle
reducing air in-leakage through good maintenance
optimizing performance of air removal equipment
nitrogen blanketing during downtime periods
4-22

4.12 REFERENCES AND BIBLIOGRAPHY

1. Cycle Chemistry Guidelines for Fossil Plants: All-Volatile Treatment, Electric Power
Meeting, International Water Conference, Pittsburgh, PA, Oct 31-Nov 2, 1994.
3. M. Rziha and R. Wulff, Cycle Chemistry in Combined Cycle UnitsThe Siemens
Experience, Power Station Chemistry Conference, Newcastle, Australia, March 1113, 1998.
4. Cycle Chemistry Guidelines for Fossil Plants: Oxygenated Treatment, Electric Power
Research Institute, Palo Alto, Calif., TR-102285, December 1994.
5. Cycle Chemistry Guidelines for Fossil Plants: Phosphate Treatment for Drum Units,
Electric Power Research Institute, Palo Alto, Calif., TR-103665, December 1994.
6. R. B. Dooley and W. P. McNaughton, Boiler Tube Failures: Theory and Practice, Three
Volume Book, Electric Power Research Institute, Palo Alto, Calif., TR-105261, 1996.
7. Corrosion Fatigue Boiler Tube Failures in Waterwalls and EconomizersVolume 4,
Electric Power Research Institute, Palo Alto, Calif., TR-100455, December 1993.
8. Monitoring Cycle Water Chemistry in Fossil PlantsVol. 1 and 3, Electric Power
Research Institute, Palo Alto, Calif., GS-7556, October 1991.
9. Cycle Chemistry Corrosion and Deposition: Correction, Prevention and Control, Electric
Power Research Institute, Palo Alto, Calif., TR-103038, Final Report, December 1993.
4-23
5
CYCLES WITH ONCE-THROUGH HRSGs ON ALLVOLATILE TREATMENT (AVT)
5.1 INTRODUCTION
An overview of the all-volatile treatment (AVT) philosophy for once-through HRSGs
was given in Section 2. This Section provides cycle chemistry target values and action
levels for each monitoring point for combined cycle plants having once-through HRSGs
on AVT. This section is intended to be used by operating staff and management
personnel.
To determine whether a particular once-through HRSG should be operated on AVT or
OT, the reader is first referenced to Section 9.
The cycle chemistry diagram, Figure 5-1, presents the target values and action levels for
each monitoring point throughout the cycle.
The use of AVT for any once-through HRSG cycle is discussed in this Section. The
discussion for once-through cycles operating on OT can be found in Section 8.
The principles established in this section should serve as guidelines regardless of the
cycle configuration for which target values are to be established. For example, some
cycles may have preheaters and/or deaerators. Suitable adjustments must be made
when establishing target values for these cases.
Also, in some cycles, steam may be utilized for cogeneration or NOx control or for some
other purpose. In such cases, the target values for this steam must be established to
meet the requirements of the intended use, whatever that might be.
5-1

Cycles with Once-Through HRSGs on All-Volatile Treatment (AVT)
Steam
Target
Parameter
*
*
Flue gas
to stack
Sample
0.15
> 0.2
> 0.3
> 0.65
S/cma
Sodium, ppb
12
> 12
Silica, ppb
10
20
40
> 40
HP steam
IP steam
LP steam

To steam injection
(if used)
Target
Reheater
LP
section

Target
Sample
0.15
>0.2
> 0.3
Oxygen, ppb (switchable with CPD)
1-10
> 15
> 20
> 0.65
pH , pH unitsa
9.2-9.6
< 9.2
>9.6
Parameter
*
*
Iron, ppb
ORP, mV
>5
C or S 20 ppb
To -300
To +50
With oxygen
scavenger
Without oxygen
scavenger
HP
IP
section
Parameter
IP
LP
Steam turbine
Heat Recovery
Steam
Generator (HRSG)
>1

Condenser
Target
Parameter
S/cma
Flue gas
High
pressure
(HP) section
Sample
Air inleakage,
scfm/100 MW
Sample
C
Supplemental
firing (if used)
Air Fuel
Attemperation
feed
IP and HP
feed pump
Combustion
Electricity
turbine and
generator
Water
Steam injection
injection
from IP steam
Bypass
Condensate
polisher
(if used)
Makeup
system
Condensate
storage

Target
Parameter
*
*
Condensate pump
and LP section
feed pump
Sample
10
Silica, ppb
S/cma
0.1
T or W
300
Chemical
feed

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
Targets
N (Normal)
Legend

Footnotes
Sample Frequency
Target Values
C = continuous
W = grab, Weekly
N = Normal
1 = Action Level 1
2 = Action Level 2
3 = Action Level 3
Target
Parameter
Sample
S/cma
0.15
> 0.2
> 0.3
> 0.65
Sodium, ppb
12
> 12
Parameter
Target
*
*
Sample
C
C
0.3
20
> 0.3
40
Sodium, ppb
C or S
>3
T or W
200
> 200
= Core parameter
= Chemical feed
Figure 5-1
Cycle Chemistry Diagram for a Once-Through HRSG Unit on All-Volatile Treatment. It should be noted that this diagram does not represent exactly any operating unit. It is only illustrative for use in the chemistry
cycle diagrams for once-through HRSG units. Operators should apply the parameter/target boxes to their actual unit.
5-3

Specific Conductivity S/cm at 25C

10.0 ppm
NH3
20
5.0
10
2.0
8
1.0
6
5
0.5
4
3
0.2
2
0.1
1.0
0.8
0.05
0.6
0.5
0.4
0.3
0.02
0.2
0.01
0.1
7.50
7.75
8.00
8.25
8.50
8.75
9.00 9.25
pH at 25C
9.50
9.75
10.00 10.25 10.50
Figure 5-2
Theoretical Relationship Between Specific Conductivity and pH for Ammonia
Solutions.
5-5

Feedwater systems having carbon steel piping, common to HRSGs, are required to
operate at a pH of 9.2-9.6 (77F, 25C) to minimize flow-accelerated corrosion. This pH
requires the addition of 500-2200 ppb of ammonium hydroxide as NH 3 (Figure 5-2).
This is sufficiently high that the polishers, for economic and regenerant waste disposal
reasons, have to be operated normally in the ammonium form and/or beyond the
ammonia break for the deep-bed cation resins. Many operators maintain stand-by resin
beds in the hydrogen form to use during periods of condenser leakage. Powdered
resins (having low ion exchange capacity) are normally operated in the ammonium
form. Ammonium form operation reduces the efficiency of mixed bed ion exchangers
especially for sodium removal from the condensate, although continuing to efficiently
remove both iron and copper corrosion products from the condenser (if copper
containing condensers are utilized).
This section will not address oxygenated treatment which solves many of these
problems and is covered in Section 8.
5.2 AVT GUIDANCE

Similarly designed once-through HRSGs may behave differently in response to
impurity ingress and feedwater corrosion product ingress because of differences in preboiler systems, balance-of-plant designs and materials choices, differences in makeup
system designs and operation, variable effectiveness of air-removal equipment and
variable avoidance of cooling water in-leakage control.
The deposition of pre-boiler corrosion product oxides in the tubing of once-through
HRSGs is critical and it plays a key part in a number of BTF mechanisms (1). In the long
term, the accumulated deposits must be removed by timely chemical cleaning. This
should be the basis of the optimization of AVT and is, of course, one of the reasons for
choosing or converting to OT (Section 8).
Here it is suggested that the road map approach described in Section 9 should be
followed to optimize the units feedwater treatment.
Target Values
established for those plants having once-through HRSGs. The following figures show
the target values and action levels for each sample point and monitoring parameter:
pH versus ammonia (Figure 5-3)
5-6

Ammonia (ppm NH3)
10
9
8
7
6
5
4
3
2
2.0 ppm CO2
1.0 ppm CO2
0.5 ppm CO2
0 ppm CO2
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
8.8
9.0
9.2
9.4
pH at 25C
9.6
9.8
10.0
Source: Adapted from unpublished NUS Corporation data
Figure 5-3
Ammonia Concentration vs. pH for Various Carbon Dioxide Concentrations
5-7

Copies of Figure 5-1, modified if necessary to reflect specific unit characteristics and/or
experience, could be included in the plant operating procedures and prominently
displayed in the control room, water and steam sample room, and chemistry
laboratory. Copies could also be displayed at the makeup treatment system control
panel and the condensate polisher control panel (if applicable). It may be more
5.3 NORMAL OPERATION FOR ONCE-THROUGH HRSG UNITS ON AVT

AVT chemistry control has historically included the injection of ammonium hydroxide
(NH4OH) for pH control and hydrazine (N2H4) for dissolved oxygen control. The
optimum pH control range is 9.2-9.6 (77F, 25C). This requires 500-2200 ppb of
ammonia as NH3 (See Figures 5-2 and 5-3) in the absence of carbon dioxide. If
hydrazine is used, it is usually controlled at the economizer inlet up to a maximum of
20 ppb.
More recently, the optimum chemistry for all-ferrous feedwater systems was evaluated
and the results question the usefulness of the hydrazine additive (or other reducing
agents) at normal operation(3). The iron level at the economizer inlet of units tested was
less without the addition of hydrazine as a reducing agent. This new AVT is
optimized without reducing agents.
Reagent grade chemicals are recommended to avoid any unknown contamination from
chemical additions. Hydrazine is a suspected carcinogen and should be added as a
35% solution or less to avoid flash-point. Proper protective gear should be utilized
when handling this material. Reaction rates with dissolved oxygen have been
studied(2).

Air in-leakage is a concern as it can affect condensate polisher anion capacity due to
carbon dioxide removal and, of course, also affects condenser discharge dissolved
oxygen concentrations.
Condenser cooling water in-leakage, makeup water contamination, condensate storage
tank contamination and improper condensate polisher regeneration can also be sources
of contaminants. Three typical examples are:
chloride or sulfate excursions due to condenser in-leakage,
caustic or acid contamination from makeup (or condensate polisher) regenerant, or
5-8

Also in combined cycle units there is a question of condensate returns which may be
contaminated.
Satisfactory operation of once-through steam generators and the associated turbine
requires that the total feedwater solids be less than 50 ppb(4).
These AVT Guidelines suggest that maximum normal operation levels should be: iron
< 5 ppb, copper < 2 ppb, oxygen 1-10 ppb, sodium < 3 ppb, and cation conductivity <
0.15 S/cm. During a contamination period, firing should be stopped if the cation
conductivity exceeds 2.0 S/cm for 5 minutes or 5.0 S/cm for 2 minutes. Some
utilities have also adopted a sodium limit for shutdown for conventional units.

During startup, the effect of chemistry control impacts on the potential for fluid-side
deposits, corrosion and impeding of heat transfer (tube metal overheating). Focus
should be directed towards the identification and correction of the root cause of the
chemical control problem for the following.
Cold Start
A key requirement during startup is to maintain adequate flow in the HRSG tubes to
protect them from overheating during both startup and low-load operation.
Hot Start
It is suggested that efforts should be made to meet a cation conductivity of < 1.0 S/cm
for two minutes and the iron level should be < 50 ppb before load is raised on the unit.
Operation should be stopped if cation conductivity exceeds 2.0 S/cm for five minutes
or 5 S/cm for two minutes.
5.6 REFERENCES
1. R. B. Dooley and W. P. McNaughton, Boiler Tube Failures: Theory and Practice,
Three Volume Book, Electric Power Research Institute, Palo Alto, Calif., TR-105261,
1996.
2. N. L. Dickinson, D. W. Felgar and E. A. Pirsh, An Experimental Investigation of
Hydrazine-Oxygen Reaction Rates in Boiler Feedwater, Proceedings of the
American Power Conference, Vol. XIX, 1957.
5-9

Meeting, International Water Conference, Pittsburgh, PA, Oct 31-Nov 2, 1994.
4. Steam, Its Generation and Use, Babcock & Wilcox, a McDermott Company,
Barberton, Ohio, 40th Edition, 1992, Chapters 42-43.
5-10
6
CYCLES WITH DRUM HRSGs ON CAUSTIC
TREATMENT (CT)
6.1 INTRODUCTION TO CAUSTIC TREATMENT

With all-volatile treatment, ammonia (and sometimes hydrazine) is added to the
feedwater to provide chemical conditions that protect the feedwater heaters, boiler,
superheater, reheater and turbine against corrosion, without further chemical
additions.
All-volatile treatment can be used for HRSG drum-type boilers, provided high purity
feedwater is available and the build-up of impurities in the boiler water is strictly
controlled (Section 4). However, ammonia is a poor alkalizing agent and does not give
much protection against corrosion, due to the ingress of corrosive salts, or to flowaccelerated corrosion, which tends to occur over the range 130-180C (266-356F). Flowaccelerated corrosion is particularly prevalent in the low pressure stages of HRSGs,
which operate in this temperature range (see Section 1.10).
The addition of a solid alkalizing agent, such as tri-sodium phosphate or sodium
hydroxide, reduces the effects of corrosive impurities and flow-accelerated corrosion.
Phosphate treatment is prone to hideout and hideout return and is difficult to monitor
and control, but is not as destructive as sodium hydroxide if dryout occurs in the HRSG
tubing, or if HRSG water impurities and conditioning chemicals are carried over into
the steam.
Caustic treatment has been used successfully in conventional coal and oil fired plants
to reduce the risk of on-load corrosion and hydrogen damage, due to acidic chloride
attack. It is being used on HRSGs for controlling flow-accelerated corrosion in LP
circuits, where all-volatile treatment has proved ineffective and phosphate treatment
has been unsatisfactory, due to hideout or difficulties of monitoring and control.
However, the addition of sodium hydroxide to the HRSG water has to be carefully
controlled to reduce the risk of caustic gouging in the tubing and carryover into the
steam, which could lead to damage of the steam circuit and turbine due to stress
corrosion(1). Caustic addition can be linked to chloride concentration for effective
6-1

Cycles with Drum HRSGs on Caustic Treatment (CT)
inhibition of acidic chloride corrosion. Caustic treatment is easy to monitor and, the
absence of the complications due to the presence of phosphate, allows on-line specific
and cation conductivity measurements to be used for control purposes.
Preliminary guidance on the use of caustic treatment of the boiler water of
conventional fossil plants was published in an EPRI(2) report on Sodium Hydroxide
for Conditioning the Boiler Water of Drum-Type Boilers in 1996. 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 coal fired drum units.
Guidance on the application, experience, benefits, limitations and implementation of
caustic treatment was included in the report(2) and additional information on the use of
caustic treatment was included in the EPRI report on Selection and Optimization of
Boiler Water and Feedwater Treatment of Fossil Plants(3).
Many of the features for the feedwater and steam for all-volatile treatment (AVT) for
drum boilers, will also apply to caustic treatment (CT). However, these need to be
supplemented by additional considerations for the HRSG water and steam.
To determine whether a particular HRSG drum cycle should be operated on CT, the
reader is first referenced to Section 9 and advised to follow the HRSG Boiler Water
Selection procedure outlined in the road map (Figure 9-5). It is particularly important
that CT will only be used on units with good circulation, and where there is no
possibility of dryout. Again the operator is referenced to the road map in Section 9.5
(Steps 13 and 22).
of cycles presently available and those under development, it is not possible to include
each in these guidelines. The cycle diagram which was chosen for the presentation of
target values and action levels for drum units is one of the more complex available,
having three drums, each operating at different pressure. The cycle diagram for CT is
presented in Figure 6-1. No differentiation is made between reheat and non-reheat
units on CT (Section 2.6).
6.2 GUIDELINES FOR CAUSTIC TREATMENT

With caustic treatment, the concentration of sodium hydroxide in the boiler water has
to be carefully controlled. There should be sufficient alkalinity to minimize the
corrosive effects of salt impurities and inhibit flow-accelerated corrosion in high flow
rate or turbulent zones at critical temperatures. However, there should not be so much
sodium hydroxide that there is a risk of caustic gouging of the HRSG tubing or stress
corrosion in the turbine, due to carry over into the steam. (Note that in the past, some
examples of gouging of waterwall tubes in conventional boilers, using high or
6-2

insufficiently well controlled congruent phosphate treatment, previously ascribed to

caustic gouging, are now known to be due acid phosphate corrosion. Both forms of
attack have a similar appearance, but the deposits contain maricite with acid phosphate
corrosion(4).)
A minimum amount of sodium hydroxide in the HRSG boiler water is required to
achieve the recommended boiler water pH and provide protection against corrosion.
The maximum amount of sodium hydroxide that should be present to avoid caustic
gouging is determined by the concentration factor at the HRSG water/tube interface.
The concentration factor depends on the type of plant, the heat transfer, the flue gas
temperature, and operating conditions, and can be capable of producing high
concentrations and pH values(1). Areas of dryout would be even worse. The
concentration factor is likely to be plant specific and, generally, is not known. However
in practice, such problems can normally be avoided simply by setting an upper limit to
the boiler water pH and, hence, boiler water sodium hydroxide concentration.
The upper limit for sodium and other salts in the HRSG boiler water is set by both the
allowable concentrations in the boiler water and the steam. As explained in Section 2,
both vaporous and mechanical carryover occurs in HRSG drum boilers. Vaporous
carryover of sodium hydroxide is unlikely to be a major problem, since it has a
volatility similar to sodium chloride and sodium phosphate. However, HRSGs can be
less sophisticated than conventional boilers, with simpler steam separation systems,
giving greater mechanical carryover. A strict limit for sodium in steam is required to
reduce the risk of stress corrosion in the turbine.
In order to reduce the risk of corrosion from impurities in the HRSG boiler water, the
concentration of sodium hydroxide in the boiler water should be linked to the chloride
concentration. A minimum concentration of sodium hydroxide is required to achieve
the recommended pH. Under normal operating conditions, the concentration of sodium
hydroxide in the HRSG boiler water can be increased so that it is 2.5 times the chloride
concentration, up to that set by the upper pH limit. This results in a band of operating
conditions, with upper and lower limits for pH and sodium hydroxide.
The normal operating limits for chloride are set by the neutralizing capacity of the
sodium hydroxide. The limits for sulfate are linked to the limits for chloride. The
corresponding limits for sodium, and specific and cation conductivity can be derived
from this data and used to assist in chemical control. EPRI Action Levels 1, 2 and 3
can then be added for each of the control parameters. It should be noted that for CT a
factor of less than 2x is used to allow a practical normal operational band or limit to
be achieved with reasonable action level safety limits. (See discussion in Section 2.5.)
Target values and action levels are presented as a continuum over a range of operating
pressures in Figures 6-2 to 6-9. As mentioned in Section 2, cycle contamination values
for the minimum HRSG boiler pressure of 600 psi (4.1 MPa) given in the curves should
6-3

be used for boilers operating below 600 psi (4.1 MPa). Since it is necessary to maintain
strict limits for impurities in steam with caustic treatment, these values should also be
used for non-reheat plants.
6.3 TARGET VALUES FOR PLANTS ON CAUSTIC TREATMENT

The sample points, monitoring parameters, target values and action levels were
developed for plants with reheat, but they are also generally applicable for those
without reheat. The following figures show the target values and action levels for each
sample point and monitoring parameter:
Cycle chemistry diagram (Figure 6-1)
HRSG boiler water primary control parameters:
pH versus operating pressure (Figure 6-2)
cation conductivity versus operating pressure (Figure 6-3)
specific conductivity versus operating pressure (Figure 6-4)
HRSG boiler water limits (it should be noted that the limits and curves for sodium,
chloride, sulfate, sodium hydroxide, and silica are provided for troubleshooting,
commissioning, and for the monitoring campaigns described in Section 9.5).
sodium hydroxide versus operating pressure (Figure 6-5)
chloride versus operating pressure (Figure 6-6)
sulfate versus operating pressure (Figure 6-7)
sodium versus operating pressure (Figure 6-8)
silica versus operating pressure (Figure 6-9)
It should be noted here that the contaminant pressure curves have only been extended
to about 2100 psi (15 MPa) for CT to indicate that at present this is the considered safe
operating limit.
Copies of Figures 6-1 to 6-9, modified if necessary to reflect specific unit characteristics,
as explained in Section 2 and/or experience, should be included in the plant operating
procedures and prominently displayed in the control room, water and steam sample
room, and chemistry laboratory. Copies of Figure 6-1 could also be displayed at the
makeup treatment system control panel and the condensate polisher control panel (if
applicable).
It may be more convenient to develop a separate figure, based on Figure 6-1, which
only includes the core parameters for the specific HRSG unit.
6-4

Target
Sample
9.2-9.6
< 9.2
> 9.6
0.2
0.35
0.65
> 0.65
Iron, ppb
Oxygen, ppb
>5
1-10
> 15
> 20
Parameter
pH
a
a
*
*
C or S
< 20
To -300
With oxygen
scavenger
Without oxygen
scavenger
To +50
Target
Parameter
Target
Parameter

ORP, mV

Saturated Steam
Sample
S/cma
0.2
0.35
0.6
>0.6
Sodium, ppb
10
>10
Silica, ppb
*
*
Sample
Sodium, ppb
>3
5
>5
10
>10
S/cma
0.2
0.35
0.6
>0.6
10
>10
20
>20
40
>40
Silica, ppb
Deaerator
HP SH steam
IP SH steam
LP SH steam
Boiler
water
chemical
feed
Chemical
feed
LP
drum
Flue gas
to stack
IP SH steam
Chemical
feed
IP
drum

To steam injection
(if used)
Target
Parameter
Reheater
HP
drum
HP
Intermediate
pressure
(IP) section
>1
Target
IP
LP
Steam turbine
Parameter
Condenser
Makeup Treatment System Effluente

Target
*
*
Supplemental
firing (if used)
Air Fuel
High
pressure
(HP) section
Sample
Cation conductivitya
or sodium
Flue gas
Low
pressure
(LP) section

Heat Recovery
Steam
Generator (HRSG)
Preheater
Sample
Air inleakage,
scfm/100 MWe
Parameter
Sample
Silica, ppb
10
0.1
S/cma
T or W 300
Boiler Water
Sample
Sodium, ppm
Immediate
Shutdown
Chloride, ppb
Silica, ppb
pHa
<8
Specific conductivity, S/cma
C or D
Parameter
*
*
*
Target

NaOH, ppm
Deaerator
pump
LP
blowdown
IP
blowdown
HP
blowdown
Attemperation
feed
Feedwater
pump
Feedwater
Chemical feed

Combustion
Electricity
turbine and
generator
Water
Steam injection
injection
from IP steam
Bypass
Condensate
polisher
(if used)
Condensate
storage
Makeup
system
Condensate
pump
Base Load
Targets
N (Normal)
1 (Action Level 1)
Cycling
336 ( 2 weeks)
672 (4 weeks)
2 (Action Level 2)
48 (2 days)
96 (4 days)
3 (Action Level 3)
16
Immediate Shutdown
Target
Sample
Plants with
polisher
>6
Plants without
polisher
12
> 12
Parameter
*
Parameter
Footnotes
Legend
Sample Frequency
Target Values
C = continuous
W = grab, once per week
N = Normal
1 = Action Level 1
2 = Action Level 2
3 = Action Level 3
Sodium, ppb
Plants with
polisher
0.3
> 0.3
Plants without
polisher
0.2
0.35
0.65
> 0.65
T or W
200
> 200
C or S
20
40
> 40
a=
b=
c=
e=

See plant specific curves
Target values may be adjusted to reflect capabilities of
installed equipment
Target
Sample
Sodium, ppb
12
> 12
S/cma
0.2
> 0.2
*
*
S/cma
= Core parameter
= Continuous sample
= Chemical feed
Figure 6-1
Cycle Chemistry Diagram for an HRSG Drum Unit on Caustic Treatment (Plants with Reheat). It should be noted that this diagram does not represent exactly any operating unit. It is only illustrative for use in the
chemistry cycle diagrams for drum type HRSG units. Operators should apply the parameters/target boxes to their actual unit. These may need customization according to Sections 1.11 and 9.5.
6-5

6.4 NORMAL OPERATION FOR CAUSTIC TREATMENT

With caustic treatment, it is particularly important to avoid dryout in the HRSG boiler
and carryover of boiler water impurities and conditioning chemical into the steam.
Careful monitoring and control of the HRSG boiler water pH, specific and cation
conductivity measurements and if possible also chloride should be undertaken using
on-line instruments. Sodium in steam should also be carefully monitored using an online instrument.
Figure 6-10 shows the relationship between specific conductivity, cation conductivity
and pH for HRSG boiler water with caustic treatment. With CT, the contribution of
anionic impurities (e.g. chlorides and sulfates) to the specific conductivity can be
obtained directly from the cation conductivity, since there is no complicating anion
such as phosphate present. The specific conductivity, after correction for the
contribution for the anionic impurities, as indicated by the cation conductivity, can then
be used as an indication of the pH. Conductivity measurements can often give a more
reliable indication of pH than direct measurements and, in any case, should be used to
confirm the value given by the pH meter.
6-7

Drum Pressure (MPa)
4.8
6.2
7.6
9.0
10.3
11.7
13.1
14.5
1300
1500
1700
1900
2100
10.2
Action level 3
10.1
Action level 2
10.0
Action level 1
9.9
9.8
Normal band
pH
9.7
9.6
9.5
Action level 1
9.4
Action level 2
9.3
Action level 3
9.2
9.1
600 700
900
1100
Figure 6-2
Caustic Treatment: HRSG Boiler Water pH vs. Operating Pressure
(HRSG/Combined Cycle Plants)
6-8

Drum Pressure (MPa)
4.8
100
90
6.2
7.6
9.0
10.3
11.7
13.1
14.5
1300
1500
1700
1900
2100
Action level 3
80
70
60
Action level 2
50
Cation Conductivity (S/cm)
40
Action level 1
30
20
Normal band
10
9
8
7
6
5
4
3
600 700
900
1100
Figure 6-3
Caustic Treatment: Boiler Water Cation Conductivity vs. Operating Pressure
6-9

Drum Pressure (MPa)
4.8
6.2
7.6
9.0
10.3
11.7
13.1
14.5
1700
1900
2100
100
90
80
70
Action level 3
60
50
Action level 2
40
Specific Conductivity (S/cm)
Action level 1
30
20
Normal band
10
9
8
Action level 1
7
6
5
Action level 2
Action level 3
3
600 700
900
1100
1300
1500
Figure 6-4
Caustic Treatment: Boiler Water Specific Conductivity vs. Operating Pressure
6-10

Drum Pressure (MPa)
4.8
6.2
7.6
9.0
10.3
11.7
13.1
14.5
1300
1500
1700
1900
2100
10
9
8
7
Action level 3
6
5
Action level 2
Sodium Hydoxide (ppm NaOH)
Action level 1
Normal band
2
Action level 1
Action level 2
1.0
0.9
0.8
Action level 3
0.7
0.6
0.5
0.4
0.3
600 700
900
1100

Normal operation.Minimum NaOH = 2.5 x chloride concentration
Action levels 1-3. Minimum NaOH = 2.5-1.5 x chloride concentration
Figure 6-5
Caustic Treatment: Boiler Water Sodium Hydroxide vs. Operating Pressure
6-11

Drum Pressure (MPa)
4.8
6.2
7.6
9.0
10.3
11.7
13.1
14.5
1300
1500
1700
1900
2100
10
9
8
7
6
5
4
Action level 3
Chloride (ppm Cl)
Action level 2
2
Action level 1
1.0
0.9
0.8
0.7
0.6
Normal band
0.5
0.4
0.3
0.2
600 700
900
1100
Figure 6-6
Caustic Treatment: HRSG Boiler Water Chloride vs. Operating Pressure
6-12

Drum Pressure (MPa)
4.8
6.2
7.6
9.0
10.3
11.7
13.1
14.5
1300
1500
1700
1900
2100
10
9
8
7
6
Action level 3
5
4
Action level 2
Sulfate (ppm SO4)
Action level 1
1.0
0.9
0.8
0.7
0.6
Normal band
0.5
0.4
0.3
0.2
600 700
900
1100
Figure 6-7
Caustic Treatment: Boiler Water Sulfate vs. Operating Pressure (HRSG/Combined
Cycle Plants)
6-13

Drum Pressure (MPa)
4.8
6.2
7.6
9.0
10.3
11.7
13.1
14.5
1100
1300
1500
1700
1900
2100
10
9
Action level 3
8
7
6
Action level 2
5
Action level 1
Sodium (ppm Na)
2
Normal band
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
600 700
900
Figure 6-8
Caustic Treatment: Boiler Water Sodium vs. Operating Pressure (HRSG/Combined
Cycle Plants)
6-14

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
20
15
10
8
7
6
5
4
3
Silica (ppm SiO2)
Action
level 3
1.0
0.8
0.7
0.6
0.5
Action
level 2
0.4
Action
level 1
0.3
0.2
Normal
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 6-9
Caustic Treatment: Boiler Water Silica vs. Operating Pressure (HRSG/Combined
Cycle Plants)
6-15

60
pH 10.2
50
pH 10.1
pH 10.0
Specific Conductivity (S/cm)
40
pH 9.9
30
20
pH 9.8
pH 9.7
pH 9.6
pH 9.4
pH 9.2
10
0
0
10
20
30
40
50
60
70
Figure 6-10
Relationship between Specific Conductivity, Cation Conductivity and pH at 25C
for HRSG Boiler Water with Caustic Treatment
6-16
80

The chloride concentration can be determined by analyzing samples of HRSG boiler

water, or preferably by using an on-line instrument. If the proportion of chloride in the
total anions of the boiler water is known to be steady, during the various plant
operating conditions, a good indication of the chloride concentration can be obtained
from the cation conductivity.
The equivalent sodium hydroxide concentration can be determined by titration of
samples of HRSG boiler water, or derived from the boiler water pH - see Figure 6-11.
suspended oxide in the boiler water.
Copies of Figures 6-10 and 6-11 should be included in the plant operating procedures
and prominently displayed in the control room, water and steam sample room, and
chemistry laboratory.

Condenser cooling water ingress or makeup water contamination can and will occur.
The reaction to this will depend on the nature of the contamination. Examples include:
chloride and cation conductivity excursions due to condenser in-leakage
contamination from makeup (or condensate polisher, if utilized) regenerant leakage
The reaction in all cases should be to increase blowdown, necessitating the addition of
sodium hydroxide to the boiler water to compensate for the loss and to correct for any
depression of pH. Under normal operating conditions, the injection of sodium
hydroxide should be such that it results in a concentration that is 2.5 times the
concentration of chloride in the HRSG boiler water, but should never exceed the upper
limits and action levels for the boiler water pH or sodium hydroxide concentration. It
might not be feasible to maintain this relationship when operating in action Levels 1, 2
and 3, and it may be necessary to progressively reduce the excess of sodium hydroxide,
but it should not be allowed to fall below 1.5 times the chloride concentration. The pH
should not be allowed to exceed the upper pH limit. If the HRSG boiler water pH falls
below 8.0, the boiler should be shut down immediately.
6-17

10.2
10.1
10.0
9.9
9.8
pH
9.7
9.6
9.5
9.4
9.3
9.2
9.1
0
Equivalent Sodium Hydroxide (ppm)
Figure 6-11
Relationship between pH and Equivalent Sodium Hydroxide Concentration at 25C
6-18


During startup, the effect of chemistry control impacts on the potential for internal tube
deposits and related corrosion. Focus should be directed towards the identification and
correction of the root causes of chemical control problems.
Cold Starts The ramp to full pressure is dependent on the HRSG boiler design and
boiler/turbine stress limitations. Analysis of the HRSG boiler water suspended solids
gives a measure of the magnetite inventory and the source of boiler deposits, while
silica is monitored out of concern for turbine deposition.
In order to give protection against contaminant ingress during the initial stages of
operation, the concentration of sodium hydroxide should be maintained within the
limits specified in Figure 6-5. Heavy blowdown can be maintained throughout the
startup, until contamination levels are well within the specified limits. Care should be
taken to avoid excessive sodium hydroxide concentrations and carryover of impurities
into the steam.
Hot Starts If possible, avoid making changes to the boiler chemistry and maintain
conditions within the specifications. Avoid excessive carryover of boiler water
impurities into the steam.
Unit Shutdown During shutdown, the pH, chloride, and specific and cation
conductivities should be monitored to determine whether they are within the normal
ranges specified. If they are outside these, it may be necessary to take corrective action
during storage or when next starting the unit.
6.7 APPROACH TO DEVELOPING OPTIMUM CAUSTIC TREATMENT

This subsection provides guidance on how to develop optimum caustic treatment for
HRSG drum boilers, particularly when all-volatile treatment has been found to be
inadequate for controlling flow-accelerated corrosion in LP sections, or when
phosphate treatment has been prone to hideout, or been difficult to monitor and
control.
A general road map for converting a unit to caustic treatment is given in Figure 6-12
and information on optimizing caustic treatment is given in Figure 6-13. Here, once
again it is reiterated that CT for HRSG circuits has been limited to 2100 psi (15 MPa)
(Section 6.3).
6-19

Current operation on AVT or PT
Is higher tolerance to
chloride required than
offered by AVT?
Do hideout and control

problems occur with PT?
or
Yes
No
Consider
conversion to CT
Continue with AVT

or PT
Review historical and current operating practice
Review HRSG
tube failures
Inspect HRSG tube oxide

deposits
Review turbine deposits

and failures
If required
Install additional feed and

boiler dosing equipment
Install additional boiler and

steam sampling equipment
Install additional on-line

monitoring equipment
Chemically clean
HRSG boiler
Revise chemistry operations
Revise chemistry training

Recommission on AVT, operate with 25-50% of the NaOH concentration
given in Guidelines; monitor boiler water chloride and alkalinity, steam sodium
If acceptable values
optimize operation
If NOT satisfactory return

to AVT or PT
Figure 6-12
Road Map for Conversion of HRSG/Combined Cycle Plants to Caustic Treatment
6-20

Optimize operation with caustic treatment
Monitor boiler water chloride and alkalinity, and

steam sodium under steady load conditions
If satisfactory values

to AVT or PT

steam sodium under startup conditions

to AVT or PT

steam sodium during load changes
increase NaOH dosed

to AVT or PT
Repeat program of monitoring of boiler

water and steam
obtained
If NOT satisfactory
Monitor carryover
into steam
If NaOH is lost from the

boiler water, monitor hideout
Continue monitoring
Establish data base
If hideout is excessive,
determine location with
Na24OH
Review results and decide on further course of

action and, if necessary, return to AVT or PT
Figure 6-13
Road Map to Optimize HRSG/Combined Cycle Plants on Caustic Treatment
6-21

Before using or commencing conversion to caustic treatment, it is important to be sure

that dryout does not occur in any of the HRSG evaporator tubes. When converting from
phosphate treatment, it is important to ensure that any hidden out phosphate returns to
the boiler water and can be controlled by blowdown. Carefully monitoring sodium in
steam, while still operating on phosphate, gives a good indication of whether excessive
carryover of boiler water impurities in steam is occurring. If this is the case, the boiler
may not be suitable for caustic treatment.
The following stages apply to optimizing individual HRSG drum boilers on caustic
treatment and conversion of similar boilers currently operating on all-volatile treatment
or phosphate treatment:
a) Install any additional equipment necessary for dosing sodium hydroxide into the
HRSG boiler water.
b) Install any additional sampling, sodium, chloride and conductivity equipment
necessary for monitoring the HRSG boiler water and steam.
c) Undertake a carefully monitored trial by (re)commissioning the HRSG boiler on allvolatile treatment and then adding a low concentration of sodium hydroxide to the
boiler water, e.g. quarter to half of that recommended in Figure 6-5.
d) Observe the concentrations and stabilities of the chloride and alkalinity in the boiler
water, look for loss of sodium hydroxide due to hideout or dryout, and observe the
concentration of sodium in steam, under various operating conditions, e.g. startup,
steady load, load changes.
If satisfactory values are obtained:
e) Increase the concentration of sodium hydroxide in the boiler water to the values
given in Figure 6-5.
f) Repeat d) above.
If satisfactory values are not obtained:
g) Return to all-volatile treatment, or add the lower concentration of sodium
hydroxide as in c) above and continue the trial.
If the sodium hydroxide used for dosing is lost from the boiler, this is a very serious
occurrence which may require stopping the addition of NaOH. As a minimum it is
necessary to:
h) Monitor hideout during load changes and carryover into steam.
6-22

If excessive hideout or loss from the boiler is occurring, this is also a very serious
occurrence, which may require stopping the addition of NaOH. It may be necessary to:
i) Carry out a trial using Na24OH to determine the extent and location of the hideout.
If excessive carryover into the steam is occurring:
j) Inspect the steam separation equipment for damage.
k) It may be necessary to modify the method of HRSG boiler operation (e.g. boiler
water level control) or reduce the limits for impurities and the amount of sodium
hydroxide added to the boiler water.
l) Review the results and decide on the further course of action.
If necessary:
m) Return to all-volatile treatment or phosphate treatment.
6.8 REFERENCES
1. H. G. Seipp, Caustic Induced Stress Corrosion of Superheater Tubing and Low
Temperature Steam Lines, Fifth International Conference on Cycle Chemistry in Fossil
Plants, Electric Power Research Institute, TR-108459, November 1997.
2. Sodium Hydroxide for Conditioning the Boiler Water of Drum-Type Boilers, Electric
Power Research Institute, Palo Alto, Calif., TR-105041, April 1996.
3. Selection and Optimization of Boiler and Feedwater Treatment for Fossil Plants, Electric
Power Research Institute, Palo Alto, Calif., TR-105040, March 1997.
4. R. B. Dooley and W. McNaughton, Distinguishing Features of Some Mechanisms
with Similar Appearances, Boiler Tube Failures: Theory and Practice, Vol 1, Chapter 7,
Electric Power Research Institute, Palo Alto, Calif., TR-105261-V1, 1996.
6-23
7
CYCLES WITH DRUM HRSGs ON OXYGENATED
TREATMENT (OT)
7.1 INTRODUCTION TO OXYGENATED TREATMENT FOR DRUM UNITS

An overview of the oxygenated treatment (OT) philosophy is given in Section 2. This
Section provides cycle chemistry target values and action levels for each monitoring
point for combined cycle plants having drum HRSGs on oxygenated chemistry. This
section is intended to be used by operating staff and management personnel.
To determine whether a particular HRSG drum cycle should be operated on OT, the
reader is first referenced to Section 9, and advised to follow the HRSG Boiler Water and
Feedwater Selection procedures outlined in the road maps (Figures 9-4 and 9-5).
Combustion turbine/combined cycles are available in a multitude of designs and
configurations. Because of the many varieties of cycles presently available and those
under development, it is not possible to include all of them in these guidelines. The
cycle diagram chosen for the presentation of target values and action levels for drum
units is one of the more complex available, having three individual cycles with drums,
each operating at a different pressure. This cycle diagram is presented in Figure 7-1.
In Section 1.11 the cycle diagrams were introduced and a caution was given to the
reader about possible differences between their actual cycle and the cycle used in
Figure 7-1 for illustration. For OT on HRSG drum units, it should be noted that in cases
where the IP or HP HRSG drums are fed by the feedpump from the LP drum this will
lead to higher cation conductivities in the IP and HP circuits which may not allow OT
to be used.
In Section 1 mention is made of the fact that feedwater heaters are not common in
combined cycle plants. Where they are used they are generally of corrosion resistant
materials. Nevertheless, flow-accelerated corrosion still remains a source of danger
particularly in low and intermediate pressure drum cycles. For this reason, the
application of oxygenated treatment may be advantageous in drum HRSG cycles.
7-1

Cycles with Drum HRSGs on Oxygenated Treatment (OT)
Generally, the application of oxygenated treatment in combined cycles having drum

HRSGs is possible only if three indispensable prerequisites are met:
All-ferrous metallurgy (copper alloys may be used only in condenser tubing).
Cation conductivity 0.15 S/cm (at 25C, 77F) in condensate, feedwater and
steam.
Cation conductivity 1. 5 S/cm (at 25C, 77F) in HRSG boiler water.
These prerequisites are difficult to meet in most HRSG/combined cycle designs, even
in the most recent versions, because as a rule the units do not include condensate
polishing. The situation becomes more complicated if an HRSG cycle is operated in the
cycling or peaking mode. For those units to apply OT, condensate polishing would
have to be retrofitted.
Cycle design and configuration issues could also restrict the application of OT. For
example, in cycles in which the boiler blowdown cascades from the high pressure to
intermediate pressure drum and from there to the low pressure drum, OT can probably
not be applied as a result of the increasing cation conductivity of the boiler water
particularly in the intermediate and low pressure drum systems.
All the statements and guidance dealing with OT for drum units are also valid for
drum HRSG boilers integrated in systems in which there are one or two drum boilers
together with a once-through boiler (see Section 1.2).
7.2 OXYGENATED TREATMENT GUIDANCE

Target values and action levels for key cycle parameters for drum HRSGs are presented
in Figure 7-1.
developed for those plants that have reheat. Figure 7-1 shows the target values and
action levels for each sample point and each monitoring parameter.
The primary HRSG boiler water control parameter is cation conductivity. Figure 7-2
shows cation conductivity versus operating pressure. The OT limits are independent of
pressure. The figure also shows the cation conductivity limits for the cases where a
unit operating on OT has to revert to AVT limits in the event of contamination.
7-2


Sample
0.15
> 0.2
> 0.3
> 0.65
Oxygen, ppb
30-50
pH,a
9.0-9.6
W or T
x
< 9.0
> 9.6
>5
*
*
Saturated Steam
Target
Parameter
Iron, ppb
Parameter
Target
S/cma
Silica, ppb
Sodium, ppb

Sample
0.15
> 0.2
> 0.3
10
> 10
> 20
> 40
>3
>6
> 12
Target
Parameter
*
*
Sodium, ppb
Sample
C
>3
>6
> 12
S/cma
0.15
> 0.2
> 0.3
x Action level 1 value depends on the economizer inlet/downcomer oxygen ratio.
Deaerator
HP SH steam
IP SH steam
IP SH steam
LP SH steam
Chemical
feed
Chemical
feed
LP
drum
Flue gas
to stack
Chemical
feed
IP
drum

To steam injection
(if used)

Target
Parameter
Sample
>1
Air inleakage,
scfm/100 MW
Reheater
HP
drum
HP
IP
LP
Steam turbine

Target
Heat Recovery
Steam
Generator (HRSG)
Parameter
Condenser
Sample
S/cma
Flue gas
Preheater
Deaerator
pump
LP
blowdown
Boiler Water
Parameter
*
*
pH
Low
pressure
(LP) section
Target
Sample
< 9.0
9.0-9.2 > 9.2

1.5 > 3.0 > 5.0
Immediate
Shutdown
< 7.5
Oxygen, ppb
Sodium, ppm
< 0.7 > 0.7 > 1.5 < 3.0
Chloride, ppb
125
> 10
250
420
Intermediate
pressure
(IP) section
IP
blowdown
Feedwater
pump
Supplemental
firing (if used)
Air Fuel
High
pressure
(HP) section
Combustion
Electricity
Attemperation
turbine and
feed
HP
generator
blowdown
Water
Steam injection
injection
from IP steam
Bypass
Condensate
polisher
Chemical
(if used)
feed

Target
*
*
Makeup
system
Condensate
storage
Parameter
Sample
Silica, ppb
10
S/cma
0.1
T or W
200
Condensate
pump

Base Load
Targets
N (Normal)
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
Parameter
*
Footnotes
Legend
Sample Frequency
Target Values
C =continuous
N = Normal
1 = Action Level 1
2 = Action Level 2
3 = Action Level 3
Target
Parameter
Sample
S/cma
0.15
> 0.15
Sodium, ppb
12
> 12
*
*
S/cma
Oxygen, ppb
Target
Plants with
polisher
Sample
0.3
> 0.3
C
T or W
20
50
> 50
200
> 200
= Core parameter
= Chemical feed
Figure 7-1
Cycle Chemistry Diagram for an HRSG Drum Unit on Oxygenated Treatment (Plants With Reheat). It should be noted that this diagram does not represent exactly any operating unit. It is only illustrative for use in
the chemistry cycle diagrams for drum type HRSG units. Operators should apply the parameters/target boxes to their actual unit. These may need custimization according to sections 1-11 and 9-5.
7-3

Drum Pressure (MPa)

6.2
4.8
7.6
9.0
10.3
11.7
13.1
14.5
15.9
17.2
18.6 19.6
100
90
80
70
60
50
Ac
tio
40
30
el
tio
20
lev
Ac
No
wi
th
lev
el
rm
al
Action level 3 without oxygen

2
ou
to
xy
wi
ge
th
wi
ou
to
xy
th
ou
ge
to
xy
ge
10
9
8
7
6
5
4
OT action level 2
3
OT action level 1
2
1.5
1
600 700
OT normal
900
1100 1300
1500 1700
1900 2100
2300
2500 2700 2850
Figure 7-2
Oxygenated treatment: HRSG drum boiler water cation conductivity vs. operating
pressure (HRSG/combined cycle plants with reheat)
Copies of Figures 7-1 and 7-2, modified if necessary to reflect specific unit
characteristics as explained in Section 2 and/or experience, should be included in the
plant operating procedures and prominently displayed in the control room, water
steam sample room, and chemistry laboratory. Copies of Figure 7-1 could also be
displayed at the makeup treatment control panel and the condensate polisher control
panel. It may be more convenient to develop a separate figure, based on Figure 7-1,
which includes only the core parameters for the specific HRSG unit.
The target values in Figure 7-1 are valid for both cycles with and without reheat. In
cycles in which the main or reheat steam of one or more pressure stages is not utilized
in the steam turbine (e.g., steam is used for heating, for NOx control or in another
7-5

process), more relaxed steam target values may be established. Nevertheless, the
requirements of the intended use must be met.
7.3 CONVERTING A DRUM HRSG TO OT AND/OR OPTIMIZING THE CYCLE

CHEMISTRY
Figure 7-3 shows the road map for the conversion of a drum HRSG unit to OT or for
optimizing the cycle chemistry. This process is a subset of the road map selection and
optimization procedures provided in Section 9.
Step 1Check the System Capability with Respect to Feedwater Quality
Volatile treatment (AVT or OT) operation requires very high feedwater purity. In cycles
with drum boilers, this (cation conductivity < 0.3 S/cm at 25C) can usually be
reached only in systems equipped with condensate polishers. A possible exception can
be in a unit with a tight condenser(stainless steel or titanium tubes welded in the
condenser tubesheet) and very good in-cycle deaeration.
If the system is designed or operated with a condensate polisher, or due to special
design issues even without condensate polishers but capable of producing feedwater
with cation conductivity < 0.3 S/cm, the conversion of the drum boiler to AVT or OT
can be considered. Otherwise commissioning and later operation has to occur with PT,
EPT or CT (see Section 3 and 6 for details).
Step 2Commissioning or Operation with AVT
Even if it was decided before commissioning to operate a drum HRSG on OT, the
actual commissioning should occur on AVT. The reason is the necessity to determine if
the unit can be operated on OT. The candidate drum HRSG units for OT that are
already in operation are, as a rule, operated on AVT so that in both cases (new and
already operated HRSGs) comparable conditions for the transition predominate.
Step 3Baseline Monitoring
The goal of the baseline monitoring is to determine the overall cycle condition. As well
as the core parameters, additional or diagnostic parameters are used for this purpose,
remembering that cation conductivity throughout the cycle is the most important
parameter. An important part of the baseline monitoring is the determination of the
boiler circulation ratio at different loads. This is helpful for the further determination of
the oxygen recirculation ratio.
7-6

System designed with condensate polisher
or
Step 1
Capable of maintaining feedwater CC<0.3 S/cm
Yes
Step 2
Commissioning or
operation with AVT
Step 3
Baseline monitoring problems identified?
No
Commissioning or operation
with non-volatile treatment
No
Continue AVT operation

(see section 4)
No

without reducing agent use
(see sections 4 and 9)
Yes
Optimize OT operation
Yes
Step 4
No
Feedwater reducing
agent applied?
Yes
Stop reducing agent use
Step 5
Monitoring 2 problems identified

Yes
Step 6
Transition to OT
Step 7

No
Step 8
Continue OT operation
Figure 7-3
Roadmap - Converting a drum HRSG to OT and/or optimizing the cycle chemistry
The baseline monitoring should not only be conducted during steady-state conditions,
but also during startup, peaking and cycling operation. If the results of the baseline
monitoring confirm that there are not any problems, the drum HRSG should be further
operated on AVT. If the baseline monitoring identifies problems (e.g., intolerable
corrosion product transport within the cycle), the use of the reducing agent (e.g.,
hydrazine) has to be reconsidered (Step 4).
7-7

Step 4Reducing Agent Use

The use of reducing agents in cycles with drum boilers leads very often to an increased
corrosion product transport within the cycle. An attempt should be made to improve
the cycle conditions by eliminating the reducing agent addition.
Step 5Monitoring 2
A second monitoring activity similar to that in Step 3 should clarify the influence of
operating without a reducing agent. If the overall chemistry has improved and no
further improvements are required, the drum HRSG can operate on AVT without any
reducing agent addition (see Section 4). Otherwise transition to OT should be
considered.
During this monitoring particular emphasis should be given to the cation conductivity
of the feedwater and of the boiler water (downcomer). It has to be verified during this
monitoring that the HRSG preconditions for OT operation (cation conductivity
0.15 S/cm (at 25 C) in condensate, feedwater and steam and cation conductivity
1.5 S/cm (at 25 C) in boiler water) can be reached in the tested cycle.
Step 6Transition to OT
The conversion from AVT to OT requires very careful preparations(1). The most
important preparation steps are:
Cycle Materials Review:

The materials of concern include Stellites, certain hard carbon rings, and tungsten
carbide rings. Any Stellite containing components should be identified so that these
components may be inspected prior to, and after the conversion to OT. Seats and
seals in the boiler feed pumps and condensate pumps where hard carbon or
tungsten carbide rings may be present should also be the subject of periodic
inspections. In many cases, replacement with alternate materials was necessary in
conventional fossil power plants.
Plant Chemistry Operations Review:

The cation conductivity normal target value at the economizer inlet is 0.15 S/cm
when operating on OT. Baseline monitoring (Step 3) and Monitoring 2 (Step 5)
results and the chemical operation records should be used to establish if the unit
(including the condensate polisher performance) can achieve and maintain all OT
chemistry requirements.
Instrumentation Capability Review:

Additional monitoring of oxygen content in boiler water (downcomer or
7-8

blowdown) is necessary during the transition to OT. An adequate on-line

instrument has to be available.
Chemical Feed Review:

In many cases, some modifications in the existing equipment or practice are
necessary for the conversion to OT. The ammonia dosing occurs with feed rates
which are markedly lower than those typical with AVT. In addition, an adequate
oxygen dosing system (with one or two dosing points) has to be procured and
constructed.
The actual transition to OT is very fast since there are no, or only a few feedwater
heaters upstream of the HRSG boiler in combined cycles. This causes HRSG tube
surfaces operating at temperatures below about 280C to passivate practically at the
beginning of oxygen dosing. Due to differences in temperature, the passivation of an
HRSG operated at a lower pressure will take longer than one operated at a higher
pressure.
Step 7Monitoring 3
A third monitoring activity similar to those in Step 3 and Step 5 should clarify the effect
of the conversion to OT. If the overall chemistry has improved and no further
improvements are required, the drum HRSG can continue to operate on OT. Otherwise
a thorough check of all transition activities, an elimination of all inconsistencies, and
the renewed monitoring 3 is sensible.
Step 8OT Operation
The normal operation of a drum unit occurs as described in the next subsection. The
emphasis is on the high cycle purity (feedwater cation conductivity < 0.15 S/cm at
25C and boiler water cation conductivity < 1.5 S/cm in steady-state operation).
7.4 NORMAL OPERATION FOR DRUM HRSG UNITS ON OT

Chemical Dosing
The system pH is established by ammonia dosing. Gaseous oxygen feed is suggested
for use with OT. Detailed information on the feed locations and the feed equipment
will need to be determined(1). Operation with deaerator vents closed will need to be
optimized by testing to determine how often, and when, the vents will need to be
opened(1).
7-9

Establishing the Oxygen Recirculation Ratio

Due to circulation ratio changes with drum boiler load, the oxygen concentration in
boiler water (downcomer) varies even with a constant oxygen content in the feedwater.
To ensure that the boiler water oxygen content does not exceed considerably the
normal target value of 5 ppb O2, establishing the oxygen recirculation ratio is necessary
during the introduction of OT. The oxygen recirculation ratio is calculated as the ratio
of the oxygen content at the economizer inlet to the oxygen content in the downcomer.
The corresponding measurements should be conducted at regular power intervals from
minimum to full load and the results plotted. During the measurements, the oxygen
content in feedwater (economizer inlet) should be kept in the normal target value range
(30-50 ppb). In this way, the minimum load at which the downcomer oxygen content
does not exceed the normal target value can be fixed. If necessary, the feedwater
oxygen content can be reduced to the lower value in the range to ensure that OT can be
practiced even with low load. Naturally, such results are unit specific and cannot be
applied on other similar units.
7.5 REACTION TO CONTAMINANTS IN THE HRSG BOILER CYCLE

The application of OT is dependent on feedwater purity. The most important target
values are those for cation conductivity: The target value for the feedwater cation
conductivity is 0.15 S/cm (25C), that for the boiler water (downcomer) is
1.5 S/cm (25C). When monitoring detects trends or out-of-bounds cation
conductivity values, corrective action must be taken. Chemical feed loss or overfeed are
also important issues as well as pH excursions. The required corrective actions are
discussed below.
Cation Conductivity Excursion. High cation conductivity indicates the ingress of
contaminants and must be dealt with very seriously and promptly. The actions
required in such cases are:
Cation Conductivity, S/cm (25 C)
Feedwater
Boiler Water
Action Required
<0.15
<1.5
None - continue normal operation.
>0.2
>3.0
Increase boiler blowdown.
>0.3
>5.0
Terminate oxygen feed.
Oxygen Feed Loss. Loss of oxygen feed for a short time has relatively minor impact on
the cycle condition. Nevertheless, maintenance efforts should be made to restore the
oxygen feed at the latest in three days.
Oxygen Overfeed. An oxygen overfeed could result in accelerated corrosion of the
boiler, particularly if the boiler water (downcomer) cation conductivity is higher than
7-10

the normal target value (1.5 S/cm). If the oxygen overfeed results in an increase of
the oxygen content in boiler water (downcomer) beyond the Action Level 1 value
(10 ppb O2) and is increasing, the oxygen feed should be discontinued immediately.
Ammonia Feed Loss. Ammonia feed loss is a very serious event that usually results
later in a boiler water (downcomer) pH decrease. Efforts should be made to restore

ammonia feed as soon as possible. If drum boiler pH (25C) drops below 8.0, the
termination of oxygen feed should occur immediately. Note that a boiler water
(downcomer) pH (25C) decrease to <7.5 is a reason for an immediate boiler shutdown.
Ammonia Overfeed. Ammonia overfeed is not a serious excursion requiring an
immediate action. Wasting of condenser air ejector drains or increasing deaerator
venting can help to remove excess ammonia. Note that ammonia overfeed causes an
additional loading of the condensate polishers and a subsequent shortening of polisher
runs.
pH Excursions. If the pH depression is due to other than ammonia feed loss (i.e., due
to contaminant ingress) an increase in ammonia dosing may be helpful. As a rule, a
cation conductivity increase occurs in parallel with pH depression. If drum boiler pH
(25C) drops below 8.0 or boiler water (downcomer) cation conductivity is > 5.0 S/cm
(25C), the termination of oxygen feed should occur immediately. Note that a boiler
water (downcomer) pH (25C) decrease to < 7.5 is a reason for an immediate boiler
shutdown.
If the pH increase is not due to ammonia overfeed, an ingress of contaminants (e.g.,

caustic from the makeup treatment system or the condensate polisher) is likely. An
increase of blowdown and the earliest possible elimination of the contaminant ingress
is advised. In terms of caustic contamination, an upper limit can be inferred from the
CT section of around 1.5 ppm. It is also extremely important to be cognizant of the
HRSG boiler circulation ratio and any dryout issues, as well as carryover and steam
purity when considering NaOH contamination. Refer to Section 9 for further
discussion.

Startup
A relatively quick startup after both short-term and longterm layup is a very important
advantage of OT. In units with condensate polishers, the ammonia addition begins with
the first use of condensate polishers. In units without condensate polishers, the
ammonia dosing starts as required to maintain the feedwater pH within the normal
target value range (pH at 25 C 9.0-9.6). Usually, due to possible air ingress during
layup, the feedwater and HRSG boiler water (downcomer) pH may be reduced. An
7-11

increased ammonia dosing is required until the feedwater and boiler water
(downcomer) pH is stabilized in the normal target value range.
Oxygen addition does not begin until feedwater cation conductivity falls below
0.15 S/cm (at 25C) and is continuing to downtrend, and until the boiler water
(downcomer) cation conductivity falls below <1.5 S/cm (at 25C). Emphasis is made
here that the startup as well as the shutdown and layup should be performed
absolutely without hydrazine or other reducing agent addition.
During startup, the boiler blowdown is generally increased until the boiler water cation
conductivity reaches the normal target value (at each individual boiler). After that, the
blowdown valves are positioned as intended during normal operation.
Shutdown
Short-term shutdown. Short-term shutdown 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. Shutdown of
ammonia feed occurs simultaneously with unit shutdown.
Longterm shutdown. Longterm shutdown 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 oxygen feed. The object of the increased ammonia feed rates is to achieve
a pH higher than 9.0 in the HRSG boiler water (downcomer) of all individual boilers.
Emergency shutdown. In case of an emergency shutdown for reasons of a technical
fault (e.g., defects in the electrical equipment, an HRSG 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, customary layup procedures have to be employed for prolonged
shutdowns, consistent with maintenance work to be performed during the outage.
Shutdown as a Result of a Serious Chemistry Excursion. After a shutdown forced by a
cation conductivity excursion, a unit drain and cleanup using non-contaminated water
treated according to the AVT requirements is recommended (see Section 4 for details).
With this, the standard cleanup loops including condensate polisher (if the polisher is
not the source of contamination) can be employed.
7-12

Layup
The layup procedures for all chemical treatments are described in Section 10.
Longterm layup. For longterm layup, both the dry layup and a nitrogen cap combined
with an oxygen-free (< 10 g/l oxygen) ammonia treated (pH >9) water within the
HRSG boilers are practicable.
Short-term layup. No additional measures are necessary besides those described
already in Short-term shutdown.

During cycling and peaking operation, cation conductivity excursions, oxygen content
variations, and pH excursions may occur. The responses to cation conductivity and pH
excursions, and to oxygen overfeed are discussed in Section 7.5.
Particularly during peaking operation, longer periods with slightly higher 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 cation conductivity of <0.3 S/cm (at
25C) cannot be reached because of the relatively short duration of the operating period
and the unit has to be operated without any oxygen dosing. There is a risk that such a
unit could sooner or later lose its passivation. In such cases a longer steady-state
operation with oxygen dosing and renewed cycle passivation has proven to be the best
remedy for establishing low corrosion product transport throughout the cycle.
If the operation without oxygen dosing is required for a longer period (e.g., more than
one week), then return to AVT (without hydrazine) may be satisfactory. If monitoring
indicates otherwise, then it may be advantageous to increase the boiler water pH in the
LP and IP drum circuits using either sodium hydroxide or tri-sodium phosphate dosing
into the boiler water. In this oxygen dosing-free period, the boiler water (downcomer)
pH (25C) should be kept in the range 9.3-9.6. In choosing the solid alkali for this
temporary dosing, the explanations and restrictions discussed in Chapter 6 (Drum Unit
on CT) and Chapter 3 (Drum Unit on PT) have to be taken into consideration.
Before restarting the oxygen dosing, the additional alkali dosing has to be stopped. In
case of the sodium phosphate use, the oxygen dosing can be started only when the
boiler water (downcomer) cation conductivity is <3.0 S/cm (25C) and is clearly
dropping. An increased blowdown will assist in decreasing the boiler water
(downcomer) cation conductivity.
7-13

7.8 REFERENCES
7-14
8
CYCLES WITH ONCE-THROUGH UNITS ON
OXYGENATED TREATMENT
8.1 INTRODUCTION TO OXYGENATED TREATMENT FOR ONCE-THROUGH

UNITS
An overview of the oxygenated treatment (OT) philosophy is given in Section 2. This
section provides cycle chemistry target values and action levels for each monitoring
point for combined cycle plants having once-through HRSGs on oxygenated chemistry.
This section is intended to be used by operating staff and management personnel.
To determine whether a particular once-through HRSG should be operated on AVT or
OT, the reader is first referenced to Section 9.
Combustion turbine/combined cycles are available in a multitude of designs and
configurations. Because of the many varieties of cycles presently available and those
under development, it is not possible to include all of them in these guidelines. The
cycle diagram chosen for the presentation of target values and action levels for oncethrough units has three individual cycles, each operating at a different pressure. This
cycle diagram is presented in Figure 8-1.
In Section 1 mention is made of the fact that feedwater heaters are not common in
combined cycle plants. Where they are used they are generally of corrosion resistant
materials. Nevertheless, flow-accelerated corrosion still remains a source of danger
particularly in cycles operating at a lower pressure. For this reason, the application of
oxygenated treatment is advantageous in cycles with once-through HRSGs.
Generally, the application of oxygenated treatment in combined cycles having oncethrough HRSGs is possible only if two indispensable prerequisites are met:
All-ferrous metallurgy (copper alloys may be used only in condenser tubing).
Cation conductivity 0.15 S/cm (at 25 C) in condensate, feedwater, evaporator

and steam.
8-1

Cycles with Once-Through Units on Oxygenated Treatment
Steam
Target
Parameter
Sample
0.15
> 0.2
> 0.3
> 0.65
D
C
10
3
> 10
>3
> 20
>6
> 40
> 12
S/cma
Silica, ppb
Sodium, ppb
Flue gas
to stack
HP steam
IP steam
LP steam

To steam injection
(if used)
Target
Reheater
LP
section
HP
IP
section
Parameter
*
*
Sample
0.15
> 0.2
> 0.3
> 0.65
Oxygen, ppb
30-150
pH (25C)
8.0-8.5
Iron, ppb
W or T
>5
IP
LP
Steam turbine
>1

Condenser
Target
Parameter
S/cma
Flue gas
High
pressure
(HP) section
Sample
Air inleakage,
scfm/100 MW
Heat Recovery
Steam
Generator (HRSG)

Target
Parameter
Sample
C
Supplemental
firing (if used)
Air Fuel
Attemperation
feed
IP and HP
feed pump
Combustion
Electricity
turbine and
generator
Water
Steam injection
injection
from IP steam
Bypass
Condensate
polisher
(if used)
Makeup
system
Condensate
storage

Target
Parameter
*
*
Condensate pump
and LP section
feed pump
S/cma
Silica, ppb SiO2
Sample
0.1
10
T or W
200
Chemical
feed

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
Targets
N (Normal)
Legend

Parameter
*
Footnotes
Sample Frequency
Target Values
C = continuous
N = Normal
1 = Action Level 1
2 = Action Level 2
3 = Action Level 3
Target
Parameter
Sample
S/cma
0.15
> 0.15
Sodium, ppb
12
> 12
*
*
S/cma
Oxygen, ppb
Target
Plants with
polisher
Sample
0.3
> 0.3
20
50
> 50
T or W
200
> 200
= Core parameter
= Chemical feed
Figure 8-1
Cycle Chemistry Diagram for a Once-Through HRSG Unit Operating on Oxygenated Treatment. It should be noted that this diagram does not represent exactly any operating unit. It is only illustrative for use in
the chemistry cycle diagrams for once-through HRSG units. Operators should apply the parameters/target boxes to their actual unit.
8-3

These prerequisites have already been met in operating stand-alone once-through

HRSGs as mentioned in Sections 1 and 5, and have condensate polishers within the
cycle. For the newer combined once-through/drum systems, condensate polishing will
probably also be required.
All statements and guidance dealing with OT for once-through units are valid for
single stand-alone once-through HRSGs as illustrated in Figures 1-7 and 8-1, or for
once-through HRSGs integrated in combined cycle plants with one or two drum boilers
as illustrated in Figure 1-8.
8.2 OXYGENATED TREATMENT GUIDANCE

Target values and action levels for key cycle parameters for once-through HRSGs are
presented in Figure 8-1.
developed for those plants that have reheat. Figure 8-1 shows the target values and
action levels for each sample point and each monitoring parameter.
Copies of Figure 8-1, modified if necessary to reflect specific unit characteristics as
explained in Section 2 and/or experience, should be included in the plant operating
procedures and prominently displayed in the control room, water steam sample room,
and chemistry laboratory. Copies of Figure 8-1 could also be displayed at the makeup
treatment control panel and the condensate polisher control panel. It may be more
convenient to develop a separate figure, based on Figure 8-1, which includes only the
The target values in Figure 8-1 are valid for both cycles with and without reheat. In
cycles in which the main or reheat steam of one or more pressure stages is not utilized
in the steam turbine (e.g., steam is used for heating, for NO x control or in another
process), more relaxed steam target values may be established. Nevertheless, the
requirements of the intended use must be met.
8.3 CONVERTING A ONCE-THROUGH HRSG TO OT AND/OR OPTIMIZING

THE CYCLE CHEMISTRY
Figure 8-2 shows the road map for the conversion of a once-through HRSG to OT or for
optimizing the cycle chemistry. This process is a subset of the road map selection and
optimization procedures provided in Section 9.
8-5

Step 1

or
Capable of maintaining feedwater CC<0.15 S/cm
Yes
Step 2
Commissioning or
operation with AVT
Step 3
Baseline monitoring problems identified?
No
Commissioning or operation
with AVT (section 5)
No

(see section 5)
No

without reducing agent use
(see section 5 and 9)
Yes
Optimize OT operation
Yes
Step 4
No
Feedwater reducing
agent applied?
Yes
Stop reducing agent use
Step 5

Yes
Step 6
Transition to OT
Step 7

No
Step 8
Continue OT operation
Figure 8-2
Road MapConverting a Once-Through HRSG to OT and/or Optimizing the Cycle
Chemistry
Step 1Check the System Capability with Respect to Feedwater Quality

Volatile treatment (AVT or OT) operation requires very high feedwater purity. As a
rule, the indispensable quality (cation conductivity < 0.15 S/cm at 25C) can be
reached only in systems equipped with condensate polishers. A possible exception is a
system with a tight condenser(stainless steel or titanium tubes welded in the
condenser tubesheet) and very good in-cycle deaeration.
8-6

If the system is designed or operated with a condensate polisher or due to special

design issues even without condensate polishers but capable of producing feedwater
with cation conductivity < 0.15 S/cm, conversion of the once-through boiler from AVT
to OT can be considered.
Step 2Commissioning or Operation with AVT
Even if it was decided before commissioning to operate a once-through HRSG on OT,
the actual commissioning should occur on AVT. The reason is the necessity to
determine if the unit can be operated on OT. Once-through HRSGs which are already
in operation will be operated on AVT so that in both cases (new and already operated
HRSGs) comparable conditions for the transition predominate.
Step 3Baseline Monitoring
The goal of the baseline monitoring is to determine the overall cycle condition. As well
as the core parameters, additional or diagnostic parameters are used for this purpose,
remembering that cation conductivity throughout the cycle is the most important
parameter. The baseline monitoring should not only be conducted during steady-state
conditions, but also during startup, peaking and cycling operation. If the results of the
baseline monitoring confirm that there are not any problems, the HRSG should be
operated further on AVT. If the baseline monitoring identifies problems (e.g.,
intolerable corrosion product transport within the cycle), the use of the reducing agent
(e.g., hydrazine) has to be reconsidered (Step 4).
Step 4Reducing Agent Use
The use of reducing agents in cycles with once-through boilers leads very often to an
increased corrosion product transport within the cycle. An attempt should be made to
improve the cycle conditions by eliminating the reducing agent addition.
Step 5Monitoring 2
A second monitoring activity similar to that in Step 3 should clarify the influence of
operating without a reducing agent. If the overall chemistry has improved and no
further improvements are required, the once-through HRSG can operate on AVT
without any reducing agent addition (see Section 5). Otherwise transition to OT should
be considered.
8-7

Step 6Transition to OT
The conversion from AVT to OT requires very careful preparation(1). The most
important preparation steps are
Cycle Materials Review:

The materials of concern include Stellites, certain hard carbon rings, and tungsten
carbide rings. Any Stellite containing components should be identified so that these
components may be inspected prior to, and after the conversion to OT. Seats and
seals in the boiler feed pumps and condensate pumps where hard carbon or
tungsten carbide rings may be present should also be the subject of periodic
inspections. In many cases, replacement with alternate materials was necessary in
conventional fossil power plants.
Plant Chemistry Operations Review:

The cation conductivity normal target value at the economizer inlet is 0.15 S/cm
when operating on OT. Baseline monitoring (Step 3) and Monitoring 2 (Step 5)
results and the chemical operation records should be used to establish if the unit
(including condensate polisher performance) can achieve and maintain all OT
chemistry requirements.
Chemical Feed Review:

In many cases, some modifications in the existing equipment or practice are
necessary for the conversion to OT. The ammonia dosing occurs with feed rates
which are markedly lower than those typical with AVT. In addition, an adquate
oxygen dosing system (with one or two dosing points) has to be procured and
constructed.
The actual transition to OT is very fast since there are no, or only a few feedwater
heaters upstream of the HRSG boiler in combined cycles. This causes HRSG tube
surfaces operating at temperatures below about 280C to passivate practically at the
beginning of oxygen dosing. Due to differences in temperature, the passivation of an
HRSG operated at a lower pressure will take longer than one operated at a higher
pressure.
Step 7Monitoring 3
A third monitoring activity similar to that in Step 3 and Step 5 should clarify the effect
of the conversion to OT. If the overall chemistry has improved and no further
improvements are required, the once-through HRSG can continue to operate on OT.
Otherwise a thorough check of all transition activities, an elimination of all
inconsistencies, and the renewed monitoring 3 is sensible.
8-8

Step 8OT Operation

The normal operation of a once-through HRSG unit occurs as described in the next
subsection. The emphasis is on the high cycle purity (feedwater cation conductivity
<0.15 S/cm at 25C in steady-state operation).
8.4 NORMAL OPERATION FOR ONCE-THROUGH UNITS ON OT

Chemical Dosing
The system pH is established by ammonia dosing. Gaseous oxygen feed is suggested
for use with OT. Detailed information on the feed locations and the feed equipment
will need to be determined(1). Operation with deaerator vents closed will need to be
optimized by testing to determine how often, and when, the vents will need to be
opened(1).

The application of OT is dependent on feedwater purity. The most important target
values are those for cation conductivity: the target value for the feedwater cation
conductivity is 0.15 S/cm (25C). When monitoring detects trends or out-of-bounds
cation conductivity values, corrective action must be taken. Chemical feed loss or
ammonia overfeed are also important issues as well as pH excursions. The required
corrective actions are discussed below.
Cation Conductivity Excursion. High cation conductivity indicates the ingress of
contaminants and must be dealt with very seriously and promptly. The actions
required in such cases are:
Cation Conductivity, S/cm (25 C)
Feedwater
Action Required
<0.15
None - continue normal operation.
>0.2
Increase system pH to about 9.2. Continue to feed

oxygen and monitor to determine the source of the
contaminant.
>0.3
Keep cycle pH at about 9.2 and terminate oxygen feed.
Oxygen Feed Loss. Loss of oxygen feed for a short time has relatively minor impact on
the cycle condition. Nevertheless, routine maintenance efforts should be made to
restore the oxygen feed at the latest in three days. If the problem persists then the unit
should be changed to AVT (without a reducing agent).
8-9

Oxygen Overfeed. An oxygen overfeed is not a very serious event. Nevertheless, efforts
should be made to establish the correct dosing rate.

Ammonia Feed Loss. Ammonia feed loss is likewise not considered to be a very
serious event. Ammonia feed should be restored as soon as practical. During the outage
of the ammonia feed, the economizer inlet pH should be monitored more closely. If pH
should depress below 7.0 (25 C) the elimination of oxygen feed is required and the
ammonia feed should be restored promptly. In most cases the pH depression is caused
by contaminant ingress. The instructions for the cation conductivity excursion should
be followed.
Ammonia Overfeed. Ammonia overfeed is not a serious excursion requiring an
immediate action. Wasting of condenser air ejector drains or increasing deaerator

venting can help to remove excess ammonia. Note that ammonia overfeed causes an
additional loading of the condensate polishers and a subsequent shortening of polisher
runs.
pH Excursions. If the pH depression is not due to ammonia feed loss but due to
contaminant ingress, cation conductivity increases in parallel with the pH depression.

The instructions for cation conductivity excursion should be followed.
If the pH increase is not due to ammonia overfeed, an ingress of contaminants (e.g.,
caustic from the makeup treatment system or the condensate polisher) is likely. The
earliest possible elimination of the contaminant ingress is necessary.

Startup
A relatively quick startup after both short-term and longterm layup is a very important
advantage of OT. The ammonia dosing starts with the first use of condensate polishers.
The deaerator, if present, is employed as with operation on AVT (see Section 5).
Oxygen addition does not begin until the feedwater cation conductivity falls below
0.15 S/cm (at 25C) and is continuing to downtrend. Simultaneously with the
beginning of the oxygen dosing, deaerator vents will be closed. Emphasis is made here
that the startup as well as the shutdown and layup should be performed absolutely
without hydrazine or other reducing agent addition.
Shutdown
Short-term shutdown. Short-term shutdown guidance consists simply of stopping
oxygen feed at least one hour before shutdown of the unit. Deaerator vents should be
8-10

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. Shutdown of
ammonia feed occurs simultaneously with unit shutdown.
Longterm shutdown. Longterm shutdown 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 oxygen feed (if the deaerator is existing within the cycle). The object of
the increased ammonia feed rates is to achieve a pH higher than 9.0 in the whole
system.
Emergency shutdown. In case of an emergency shutdown for reasons of a technical
fault (e.g., defects in the electrical equipment, an HRSG 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, customary layup procedures have to be employed.
Shutdown as a Result of a Serious Chemistry Excursion. After a shutdown forced by a
cation conductivity excursion, a unit drain and cleanup using non-contaminated water
treated according to the AVT requirements is recommended (see Section 5 for details) .
With this, the standard cleanup loops including condensate polisher (if the polisher is
not the source of contamination) can be employed.
Layup
Guidance for proper layup for all chemical treatments is described in Section 10.
Longterm layup. For longterm layup, both the 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. As an alternative to the usual replacement of
oxygen-containing system contents with an 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 (30-150 ppb oxygen) ammonia treated (pH
8.0-8.5) water has proved to be worthwhile. The purpose of such measures is to ensure
that the optimum redox conditions are kept in the system even during the idle period.
Short-term layup. No additional measures are necessary besides those described
already in Short-term shutdown.
8-11


During cycling and peaking operation, cation conductivity excursions, oxygen content
variations, and pH excursions may occur. The treatment of these events is discussed in
Section 8.5.
Particularly during peaking operation, longer periods with slightly higher cation
conductivity than the steady-state normal operating values (i. e., >0.15 S/cm at 25C)
are not an exceptional case. In many cases, even a cation conductivity of <0.3 S/cm (at
25 C) cannot be reached because of the relatively short duration of the operating
period and the unit has to be operated without any oxygen dosing. There is a risk that
such a unit could sooner or later lose its passivation. In such cases a longer steady-state
operation with oxygen dosing and renewed cycle passivation has proven to be the best
remedy for establishing low corrosion product transport throughout the cycle. If such a
prolonged OT operation is not possible, the unit should be operated according to the
AVT guidance (Chapter 5) until a prolonged operation on OT is possible.
8.8 REFERENCES
8-12
9
APPROACH TO DEVELOPING OPTIMUM CHEMICAL
TREATMENT FOR HRSGs ASSOCIATED WITH
COMBUSTION TURBINE/COMBINED CYCLES
9.1 INTRODUCTION
As indicated in Section 1.11 (Figure 1-15), there are a number of possible combinations
of single, double, and triple pressure drum systems; single and double pressure oncethrough systems; and combination drum and once-through systems.
The previous sections (3-8) have delineated individual chemistries which can be used
for single pressure systems, either drum or once-through. It is most likely that for
multiple pressure systems that different chemistries will be optimum for each of the
pressure cycles.
The purpose of this section is to provide advice and guidance in selecting and
optimizing the feedwater and boiler water chemistries for each HRSG pressure cycle,
drum or once-through, in a unit.
This is important because there is a developing data bank of tube failures in HRSGs
which relate directly to the chemistry choice. Some of the more important tube failure
mechanisms were discussed in Section 1-10. To re-emphasize the importance of
selecting and optimizing the chemistry treatments, some of the major problem areas
that have occurred and are to be avoided are delineated here:
Flow-accelerated corrosion (FAC) especially in the LP circuits at HRSG tube bends
Under-deposit corrosion mechanisms
acid phosphate corrosion when using congruent phosphate treatment and

additions of low molar ratio phosphate chemicals. This can occur in HP circuits.
9-1

Approach to Developing Optimum Chemical Treatment for HRSGs Associated with Combustion
Turbine/Combined Cycles
Caustic gouging in regions of deposition and/or dryout if excessive NaOH is

used in CT or as an additive to counteract acidic contamination when operating
with AVT.
hydrogen damage in regions of deposition and/or dryout when acidic

contamination occurs (condenser leaks or leakage of regeneration acids)
Phosphate hideout and hideout return leading to severe chemical control problems.
If this occurs with only tri-sodium phosphate additions then no corrosion will occur;
however if mono- or di-sodium phosphate additions are made together with serious
deposition and dryout then acid phosphate corrosion can result.
Deposition of corrosion products. This could involve deposition in the HRSG of

corrosion products from pre-HRSG circuits, or deposition of NaOH on turbine or
superheater tubes.
Fouling of boiler flow distribution orifices with feedwater corrosion products can
lead to uneven flow over the steam generator tubes.
Corrosion fatigue from the fluid side of HRSG tubes.
9.2 OVERVIEW OF THE SELECTION AND OPTIMIZATION PROCESS

The overall process should first involve selecting the feedwater treatment for a new
unit (Section 9.3) and/or optimizing the feedwater for a currently operating unit
(Section 9-4). Here, because HRSG units basically have all-ferrous metallurgy, there are
three options for feedwater treatment for each of the chemistries outlined in Sections
3-8:
AVT with ammonia or an alkalizing agent (amine) and a reducing agent (oxygen
scavenger)
AVT without the reducing agent
OT
Selection or optimization of the HRSG boiler water treatment (Section 9.5) should
follow the exercise for the feedwater, which is independent of whether the HRSG has 1,
2 or 3 pressure cycles. Here, it has to be recognized that with multiple drum pressure
cycles, the optimum overall chemistry probably will involve different chemistries in the
individual cycles. Thus the selection/optimization must be accomplished accordingly
for each cycle. For once-through systems, only AVT and OT can be considered and
thus the selection/optimization process is the same as that used for feedwater.
9-2

9.3 SELECTION OPTIONS FOR FEEDWATER TREATMENT FOR HRSG

CYCLES
As indicated in Section 1, HRSGs are typically designed with all-ferrous feedwater
systems which usually involve a preheater, deaerator and connecting pipework. Thus
the pH constraints inherent with mixed metallurgy systems are removed.
It should be noted that the condenser may be tubed in a copper base alloy or titanium,
but this does not significantly affect the selection and optimization process.
Objectives for Feedwater Treatment

The main objective of the feedwater treatment with all-ferrous metallurgy is to
minimize generation and transport of iron oxides into the HRSG and turbine, and to
prevent corrosion of the pre-HRSG cycle components including the economizer or
preheater, during operation and layup.
During normal operation, the iron concentration in the final feedwater (at the
economizer inlet) should be < 5 ppb. Lower concentrations are desirable and
achievable by using the information in this subsection. Combined cycle units with aircooled condensers, however, may find it difficult to achieve this limit.
Additional objectives include:
avoidance of generation of corrosion and scale forming decomposition products
compliance with environmental regulations during operation, layup, and

discharging and handling of chemicals
Typical Feedwater Problems

The main problem is the generation of iron species containing corrosion products (iron
hydroxide, iron oxide hydrates, and iron oxides), their transport around the cycle, and
their deposition in specific cycle regions. The generation of corrosion products occurs
mainly due to corrosion and flow-accelerated corrosion of preheaters, deaerators,
economizer inlet tubing and piping, and feedwater piping.
Consequences of this primary problem include:
failure (sometimes catastrophic and fatal) of piping and tubing within the feedwater
system due to FAC
feedpump fouling
9-3

HRSG deposits which can act as centers for under-deposit corrosion mechanisms
HRSG tube failures
Flow distribution orifice fouling
frequent chemical cleans
Selection of Feedwater Treatment

In cycles with all-ferrous alloys, the following feedwater treatments could be used:
Treatment
Conditions
oxygenated
may need condensate polishers
all-volatile with:
ammonia
all situations
organic amines(1,2,3)
must be evaluated, very little experience.
All-volatile treatment with ammonia is often combined with the use of hydrazine or
another reducing agent (oxygen scavenger). In many cases, the application of a
(4)
reducing agent is not required . It has been shown that reducing or eliminating the
dosing results in a decrease of feedwater total iron content and provides protection
against flow-accelerated corrosion.
The feedwater treatments using organic amines are often (but not always) combined
with an oxygen scavenger. Generally with AVT, an alternate amine and/or an organic
based reducing agent are not desirable or needed in cycles with HRSGs.
Which of these feedwater treatments should be used and whether a reducing agent
should be used at all, can only be determined by field testing.
Decomposition of Amines and Reducing Agents. Amines other than ammonia will
thermally decompose in the HRSG and the steam circuits, forming organic acids,
carbon dioxide, and other decomposition products. This also happens to reducing
agents other than hydrazine. Corrosion and flow-accelerated corrosion effects and
removal of harmful decomposition products must be considered when selecting a
feedwater treatment. Attention also needs to be given to the concentration of reducing
agents and organics in the LP HRSG evaporator circuit. The decomposition products
may represent a corrosion risk to the turbines and may reduce the efficacy of cation
conductivity measurements for monitoring steam purity. The harmful effects of some
of the decomposition products may be reduced when condensate polishers are used,
but generally the concern is for the turbine.
9-4

Water Chemistry
In the area of water chemistry, the objectives of optimization are achieved either by
selection of a pH value in cycle streams that is high enough to minimize generation of
corrosion products in the plant cycle (pH > 9.5) or by an oxygenated treatment. With
both alternatives, controlling impurity ingress from condenser leaks and air in-leakage is
essential as well as very quickly reaching the normal guideline values during and after
each startup. An overview of the key differences between oxygenated treatment and
all-volatile treatment in conventional plants is shown in Figure 2-3.
Total organic carbon (TOC) and total halogenated organic matter (TOX) in the makeup
water or via condenser leaks from cooling water, can lead to an increase of cation
conductivity and chloride in the feedwater, and a reduction of pH. This needs to be
taken into account when selecting the method of feedwater conditioning (AVT or OT)
and the optimum method of HRSG water treatment for units with drum cycles.
All-Volatile Treatment. The basis of AVT is an elevated pH in all plant cycle streams.
The most common alkalizing agent used in AVT is ammonia. Originally, the ammonia
dosing was always combined with the hydrazine feed. Investigations performed in the
last ten years show that reducing and even eliminating hydrazine (or other reducing
agent) feed minimizes the corrosion product generation(4). Figure 9-1 illustrates the
results for an all-ferrous system.
The feedwater AVT key parameters are summarized in Sections 4 and 5.
Figure 9-2 illustrates the magnetite formation on all-ferrous feedwater materials
operating with deoxygenated AVT.
AVT with alternate amines and other oxygen scavengers could also be used in cycles
with HRSG drum boilers but are not desirable or needed. With these alternate
treatments the feedwater chemistry must be optimized through an extensive
monitoring program as discussed later.
Oxygenated Treatment. While elevated pH is the basis of AVT, oxygenated treatment
(OT) uses oxygenated high-purity water to minimize corrosion and flow-accelerated

corrosion in the pre-HRSG cycle. Oxygen, hydrogen peroxide, and air have historically
been used as oxidants; oxygen is the preferred choice. The feedwater oxygenated
treatment key parameters are summarized in Sections 7 and 8.
For the application of oxygenated treatment in units with once-through and drum
HRSGs, the one indispensable prerequisite is that the cation conductivity must be less
than 0.15 S/cm (at 25C, 77F) in the condensate, feedwater, and steam. An added
prerequisite for drum units is that the cation conductivity in the HRSG boiler water (or
9-5

downcomer) must be less than 1.5 S/cm (at 25C, 77F), with care to avoid
downcomer entrained oxygen.
The basis of the success of OT depends on the formation of a layer of ferric oxide
hydrate (FeOOH) on the surface of the magnetite oxide layer and within the pores,
which is much less soluble in feedwater than magnetite. This is illustrated in Figure
9-3.
200
50
100
40
16
14
ORP
12
N2H4 ppb
ORP mV
-100
Fe
20
-200
N2H4
Fe ppb
10
30
4
10
-300
2
-400
10
20
30
40 50 60
Time (days)
70
80
90
Figure 9-1
Changes in Oxidizing Reducing Potential (ORP) and Feedwater Iron Levels (Fe) at
the Economizer Inlet when Hydrazine (N2H4) is Gradually Reduced on a 600 MW
Drum Unit with an All-Ferrous Feedwater System.
9-6

H2O
Fluid boundary layer

Fe(OH)+
Fe(OH)+
OH-
H2
H2
Oxide
protective
cover layer
Fe3O4
H2
Epitactic
)+
Fe(OH
OH-
2+
Fe
2 Fe(OH)+
2
1
3
Topotactic
Metal
Figure 9-2
Schematic Representation of Oxide Formed on Iron-Based Feedwater Surfaces
During Operation with Deoxygenated AVT.
Fluid boundary layer

O2
H2O
Oxide
protective
cover layer
Metal
y-FeOOH or
a-Fe2O3
Fe3O4
Figure 9-3
Schematic Representation of Oxide Formed on Iron-Based Feedwater Surfaces
During Operation with OT.
9-7

Startup vs. Normal Operation. Particularly during startup, an increased corrosion
product transport occurs around the cycle. This is true mainly for feedwater systems
operated on AVT. Major improvements can be achieved by proper layup of the unit or
by operating with OT. Improvements can also be achieved by operating without an
oxygen scavenger. Layup is covered in Section 10.
Organic Feedwater Treatment Chemicals. Use of new organic feedwater treatment
chemicals (alkalizing agents and/or reducing agents) needs to be thoroughly evaluated

concerning their decomposition, monitoring, analytical interferences, and toxicity. As a
rule, none of the organic feedwater treatment chemicals are desirable or needed in
HRSG cycles with all-ferrous feedwater systems.
Sampling and Analysis. Proper sampling and analytical procedures are an essential
part of the feedwater chemistry optimization process. Suspended corrosion products

tend to adsorb on stainless sampling system tubing, plastic tubes, and grab sample
containers.
9.4 OPTIMIZATION OF FEEDWATER CHEMISTRY FOR HRSG/COMBINED

CYCLE UNITS
Figure 9-4 is a road map for optimizing feedwater treatment and for possible
consideration of converting the unit to oxygenated treatment or running the unit
without a reducing agent (oxygen scavenger). The methodology described in this
subsection is equally applicable for drum and once-through HRSG units with allferrous metallurgy. For once-through HRSG units, the optimized feedwater becomes
the circuit treatment and, as such, this subsection can also be regarded as the boiler
water optimization as well.
9-8

No current
problems
Step 1
Review normal or
current feedwater
treatment
No problems.
BUT possible
economic savings
Step 2
Monitoring
baseline
Continue use of
current treatment
Low level of
corrosion products
Step 3
Reduce oxygen
scavenger in steps
Eliminate
reducing agent
Step 4
Monitor
(as in Step 2)
Step 5
Yes
Step 6
Convert to OT. Drum
and once-through
units
Can unit
convert to OT?
No
Step 7
Step 8
Optimize feedwater
with minimum O2
scavenger
Monitor
(as in Step 2)
Figure 9-4
Road Map for Optimizing Feedwater Treatment for All-Ferrous Once-Through and
Drum Units
Step 1Review Normal or Current Feedwater Treatment

This step involves a review of the normal or current feedwater treatment. If there are
no problems, continue to use the current treatment. Such a review would indicate that:
the operating experience has been good,
minimal chemical control problems have been experienced,

9-9

no HRSG tube failures relating to waterside problems (as indicated in Sections 1.10
and 9.1) have occurred in the last five years,
no steam turbine deposition or blade failure problems have occurred, and
the feedwater is operating in the optimum fashion with minimum levels of

feedwater corrosion products.
In such cases of good experience, no changes need to be made. However, it is

suggested that the road map is reviewed as there may be considerable economic
savings to be gained by reduction or elimination of oxygen scavengers (AVT) or by
conversion to OT.
If this review is occurring prior to first operation of the HRSG, then the operator should
review the possible problems that can occur on HRSGs (Sections 1.10 and 9.1) and the
feedwater choices in Section 9.3.
Step 2Monitoring Baseline on Current Feedwater Treatment
This step involves a complete baseline monitoring to quantify the current chemical
parameters and in Step 3 to determine the need for a reducing agent. For newly
operating HRSG units this can be regarded as part of the chemistry commissioning.
This program would utilize the installed core chemistry monitoring system,
supplemented by the other parameters in the cycle chemistry diagrams. The installed
monitoring equipment should agree closely with that defined as Core Parameters
(Table 2-1).
The monitoring program should pay particular attention to the adequacy of the
makeup and chemical feed systems, condenser tightness, air ingress, and corrosion
product transport.
This monitoring involves taking a thumb-print of the HRSG unit under typical
operating conditions to identify under controlled conditions exactly how the unit
chemistry is behaving. It may involve a review of the operating chemistry logs, but this
often is not satisfactory and it is preferable to undertake a monitoring campaign.
Before this campaign is initiated, it is important to review the operators chemistry
monitoring capability and reliability. This should include Quality Assurance (Q/A)
and Quality Control (Q/C) of existing and normally utilized analytical chemistry
monitoring and analysis methodology and equipment (for example, see EPRIs Cycle
Chemistry Monitoring Program(6,7)).
9-10

Varying Operating Conditionsbase load, startup, shutdown
Steam Chemistrycation conductivity, sodium, chloride, silica and sulfate
Feedwater Chemistrycation conductivity, chloride, corrosion products (Fe, Cu),

oxygen, pH, oxidizing-reducing potential (ORP)
Boiler Watercation and specific conductivity (especially if organic feedwater

additives will be tested)
Operation of Condensate Polishers (if included)
If this step indicates a low level of feedwater corrosion product transport (such as Fe <
2 ppb) and acceptable feedwater purity from a dissolved solids standpoint with the
control chemistry meeting the guidelines values provided in Sections 3 through 8, then
it is suggested to continue with the current chemistry.
Step 3Evaluate Reducing Agent Requirements
This step is a subset of Step 2 and should involve a series of tests to minimize the
generation and transport of feedwater corrosion products.
It should be possible for HRSG units with all-ferrous feedwater systems, with proper
air in-leakage control (1.0 scfm/100 MWe (1.7 sm 3/h/100 MW)), to eliminate the
reducing agent (such as hydrazine) without jeopardizing chemistry control on the
unit(4). Thus in Step 3, a series of tests should be performed to evaluate the need for the
reducing agent and, if needed, to determine the proper agent levels. The tests should
utilize the monitoring system instrumentation (used in Step 2) while reducing or
eliminating the reducing agent dosage. Particular note should be made of dissolved
oxygen levels and the level of corrosion products generated during each test. Reference
can be made to Figure 9-1, which illustrates such a procedure. Particular attention
should be paid to the fact that there can be long lead times between changes in the
feedwater chemistry and corrosion product transport, so careful planning is needed for
accurate extended tests.
This step is extremely important and links with the boiler water optimization
procedure which needs to assess whether reducing agents (and organics) concentrate in
the LP HRSG circuits (see Step 3 on Figure 9-5).
Step 4Monitoring with New Feedwater Treatment
Step 4 involves a period of normal operation with the new feedwater treatment, which
occasionally requires repetition of monitoring (Step 2) to confirm that running with
9-11

reduced or zero reducing agent provides the optimum feedwater treatment. This
might involve a reduced monitoring effort which just looks at feedwater oxygen and
corrosion products at the economizer inlet, in parallel with the cycle core parameters,
which are normally continuously recorded and alarmed.
Steps 5 and 6OT Selection and Conversion
Once the baseline monitoring (Step 2) and a period of normal operation has been
undertaken, the question can be raised about whether the unit could run on oxygenated
treatment (Step 5). The reader is referenced to Sections 7 and 8 and to the OT
Guideline(8), which provide step-by-step guidance on whether a unit is suitable for OT
and how to convert units to OT (Step 6).
Step 7Continue to Optimize the Feedwater Treatment
This step continues the efforts in Steps 3 and 4.
Step 8Monitoring
There are now three treatments that can by used for the feedwater along with proper
pH control:
Zero reducing agent
Optimum reducing agent, and
Oxygenated treatment
The optimum treatment for each unit should be continually checked. As well as the
core parameters (Table 2-1) at the key cycle points, it is now necessary to ensure that
the operation of the deaerator vents (if used) are operated in a manner which provides
minimum levels of corrosion products in all parts of the cycle.
9.5 SELECTION OF OPTIMUM HRSG DRUM BOILER WATER TREATMENT

Here it is first assumed that the feedwater has been selected (Section 9.3), and conforms
with the recommendations given in the various chemistry sections (3 to 8), and has
been optimized according to the previous subsection (9.4).
The limits given for feedwater in the guidelines for all-volatile treatment (AVT),
phosphate treatment (PT), equilibrium phosphate treatment (EPT) and caustic
treatment (CT) are similar to one another and, therefore, the choice of the HRSG boiler
9-12

water chemical conditioning, largely reflects the tolerance to ingress of impurities, out
of specification operation, type of HRSG, maximum heat flux, and the amount of
blowdown required. Some of the major influencing factors are the cooling water for
the plant (either fresh water or saline), whether the condenser has welded titanium
tubes, whether there is a cooling tower, and whether the unit has a condensate polisher.
In the first subsection, Figure 9-5 provides a road map of the steps that should be
considered to determine the optimum HRSG boiler water treatment. This process and
thinking should first be applied to each HRSG pressure circuit individually; it has been
assembled keeping in mind the possible HRSG tube failure mechanisms and operating
problems, which were delineated in Sections 1.10 and 9.1.
Following this process through the road map, it will be necessary to consider in parallel
any possible interactions between pressure cycles, which were mentioned in Section
1.11.
Needless to say this process can and should be applied by the operator when
considering the appropriate HRSG boiler water chemistry for a new HRSG.
Once these processes have been followed and an optimum drum boiler water chemistry
has been selected, attention should then be directed to the appropriate chemistry
sections (3-8). In each of these there are various further procedures for:
a) converting from one chemistry to another, for example:
converting to EPT (Sections 3.8 and 3.9)
converting to AVT (Section 4.7)
converting to CT (Section 6.7)
converting to OT (Section 7.3)
b) further optimizing the boiler water chemistry choice, for example:
optimizing CT (Section 6.7)
9-13

1
Initial choice of operating chemistry
or
Capable of producing feedwaterCC<0.3S/cm
Yes
No
12
Commissioning/Operation
with non volatile treatment
Commissioning/operation
with volatile treatment
3
4
Baseline review and
monitoring on AVT
13
Baseline review and
monitoring on PT
Problems
5
No
problems
6
14
Is condensate polisher
used or planned?
No
Feedwater contamination
Yes
No
Yes
7
Feedwater
reducing agent?
Yes
8
No
9
Confirmatory
monitoring
17
Fresh water
cooling
Confirmatory
monitoring
10
Confirmatory
monitoring
15
Consider/
convert to
EPT
18
Saline
cooling
19
Consider/
convert to
PT or CT
16
Confirmatory
monitoring
20
Consider/
convert to
PT or CT
21
Confirmatory
monitoring
22
Dryout or
carryover
Yes
AVT
AVT
11
OT
EPT
PT
23
Normal operation
Normal operation
Figure 9-5
Road Map for Drum HRSG Boiler Water Treatment Selection
9-14
No
CT

Boiler Water Selection for Individual Drum Pressure Cycles

Step 1Initial Choice of Operating Chemistry
It has already been suggested that the road map rationale should be applied to each
single pressure drum-type HRSG and to each pressure drum-type circuit of a combined
drum/once-through unit; however, the sensible approach for initiation of the selection
is to apply one chemistry to all the pressure circuits of a unit. The primary objective of
Step 1 is to determine whether this should be an all-volatile chemistry (AVT or OT) or a
non-volatile chemistry (EPT, PT or CT). It is suggested strongly that the two choices
are AVT and PT. This is regarded as the starting position in Step 1. It may be possible
at the end of the selection process that different chemistries may be defined for the
different pressure circuits; for example PT in the LP HRSG and AVT in the HP HRSG.
Assistance with this choice can be provided with information from the feedwater and
condensate, and relates to the capability of producing good quality feedwater with
cation conductivity of less than 0.3 S/cm. If a unit has a condensate polisher and/or
can produce feedwater with cation conductivity less than 0.3 S/cm, then the choice for
commissioning or early operation of the HRSG boiler water treatment could be AVT
(starting with Step 2 and following the left hand side of Figure 9-5). If not, and it is
already known that the unit has poor feedwater and condensate chemistry due to
leakage or condensate returns, then PT should be chosen (starting at Step 12 and
following the right hand side of Figure 9-5).
If this selection process is being reviewed after the unit has been operating for some
time, then some of the key questions that need consideration are:
Historically, has the feedwater cation conductivity most often been below 0.2
S/cm? This might indicate that condenser leakage over a period of time has not
been of concern.
Can the HRSG boiler water meet the cation conductivity and chloride requirements?
Does the HRSG drum have a consistent carryover problem?
Does the unit have a condensate polisher?
Does the unit have a satisfactory monitoring system having the ability to monitor
the essential core parameters (Table 2-1) as indicated in the cycle chemistry
diagrams?
9-15

Step 2Commissioning or Operation with Volatile Treatment

If this route is followed then AVT chemistry will be the initial choice.
Step 3Baseline Review and Monitoring on AVT
If the HRSG evaporator circuit has already been operating on AVT, it is advisable to
review the operating experience to date and to answer the following questions. The
AVT may be set up incorrectly and may need changing to another treatment, or the unit
may be suitable for conversion to oxygenated treatment (OT).
Has the unit experienced any of the problems relating to the generation, transport
and deposition of feedwater corrosion products (Section 9.1)?
Does the boiler water experience pH depressions during the shutdown and early
startup periods which require the addition of either phosphate or caustic?
Are chemicals other than tri-sodium phosphate or sodium hydroxide added to the
HRSG boiler water for correction of chemical ingress?
Does the feedwater cation conductivity often and significantly rise above 0.2
S/cm?
Have FAC failures occurred in a LP HRSG circuit?
Have other HRSG tube failures occurred (Section 1.10 and 9.1)?
If the answer to any or some of these questions is positive, then maybe the AVT is not
providing optimum chemical control. It is suggested that a baseline monitoring
program is initiated to see whether the appropriate route is to optimize a volatile
treatment (Steps 5-11) or move to a non-volatile treatment (Steps 12-23).
If these reviews and those in Step 1 indicate problems or potential problems, then the
baseline monitoring will provide the key direction and should involve as complete a
program as possible, which will not only quantify the chemistry parameters, but will
also address the flue-gas side conditions and the unit flow-, and hydro-dynamics. This
program will utilize the installed chemistry monitoring systems, the core parameters
(Table 2-1), supplemented by monitoring some of the parameters under Additional
Monitoring or Diagnostic Parameters in the same table.
Varying Operating Conditionsbase load, startup, shutdown
9-16

HRSG Boiler Water Chemistry with Blowdown Open and Closedfree sodium
hydroxide, chloride, sulfate, silica, pH, cation conductivity, Fe, Cu, and carryover
Steam Chemistrycation conductivity, sodium (as a measure of both salts and free
hydroxide), phosphate, chloride, silica, sulfate, and boiler carryover of these
chemicals

products (Fe, Cu), oxygen, pH, and oxidizing-reducing potential (ORP)
Operation of Condensate Polishers (if included in cycle)
by monitoring total carryover (Section 2.6). Concern must also be given to any
contaminants introduced to the steam by way of the feedwater used for temperature
control (attemperation).
For the feedwater, there is a need to review the reducing agent usage. For all-ferrous
feedwater systems, the feedwater should be monitored with and without hydrazine
additives or other reducing agent alternatives. For units that continue to use a reducing
agent after optimizing the feedwater (Section 9.4), it is important to monitor the
concentration of the reducing agent or the oxidizing-reducing potential (ORP) in the LP
HRSG evaporator circuit. Very often the reducing agent has been found to reach very
high levels (100s of ppb) compared with normal feedwater levels, and can give rise to
very reducing HRSG boiler water conditions (ORP around 350 mV or lower). This
may be an indicator that FAC is possible in the LP circuit.
Iron levels in the HRSG drum are another good indicator of FAC and ideally should be
less than 100 ppb. In the feedwater (economizer inlet) optimum feedwater chemistry
should result in less than 5 ppb.
In terms of impurities, the cation conductivity in an HP circuit should be less than 2
S/cm, and in an LP circuit should be less than 3 S/cm.
Organics (natural, from amines, and from condensate returns) should also be checked
as these can also be very high in LP evaporator circuits. TOC should be less than 200
ppb, however, the maximum tolerable TOC has to be established by monitoring for
each steam/water cycle specifically.
The circulation ratio of the boiler should be determined. The flue gas temperature
entering the particular pressure sections should be determined as stratification of flue
gas can often vary by over 100C in each pressure section, which could be exacerbating
FAC, deposition problems, and dryout.
9-17

Steps 4 and 5Identification of Problems

The results of the review and monitoring in Step 3 should provide the subsequent
direction. The following questions should be answered from Step 3:
i)
Does the reducing agent concentrate in the LP circuit?
ii) Do organics concentrate in the LP circuit?

iii) Are iron levels higher than guideline values in the drum and feedwater?
iv) Is there excessive carryover (SiO2 > 10 ppb, Na > 3 ppb)?
v) Is the HRSG boiler water cation conductivity higher than 2 S/cm in the HP drum,
or 3 S/cm in the LP drum?
vi) Is the circulation ratio below design value?
vii) Is the flue gas severely stratified in terms of temperature distribution?
If the answer to any or all of these questions is yes, then it is strongly suggested to
consider the non-volatile road map path (Steps 4-23). One of the major reasons will be
to overcome FAC in the LP HRSG circuit.
However, if no problems are indicated or suggested from Step 3, and the monitoring
indicates compliance with the guideline values (Sections 4 and 7), then the volatile
route should be considered.
In either case, if the answer to i) and iii) is yes, then further optimization of the
feedwater may be required, especially with regards to optimum reducing agent usage
(Section 9.4).
Step 6Is Condensate Polisher Used or Planned?
Prior to making a decision to operate with, or convert to, AVT or OT, it appears
sensible to reconsider possible contaminant ingress into the cycle, and whether a
condensate polisher is available or not. This is somewhat a repeat of Step 1, however
for OT in drum HRSG cycles, it is considered as one of the precursors to have a
condensate polisher to ensure that feedwater cation conductivity will meet guideline
values.
If there is no condensate polisher, then it is necessary to review the types of possible
contaminant ingress. Information should be available from Step 3. One way of doing
this is to determine how closely the unit has met the guideline limits for feedwater, and
9-18

the amount of time, in the past (2-3 years), that the unit has been out of normal target
limits. For example, an operator might want to consider the cumulative hours
equivalent to Level 1 for economizer inlet cation conductivity as being acceptable and
controllable contamination (Figure 4-1). The operator should be looking for compliance
with the AVT guidelines in Section 4. Some operators might consider without a
polisher, that EPT offers a little more buffering capacity (Step 15). Alternatively, it may
be considered preferable to justify the inclusion/addition of a polisher in the cycle.
Step 7Feedwater Conditioning
This next important step relates back to the feedwater optimization (Step 3 in Figure 94), where for all-ferrous systems it is possible to operate with the feedwater reducing or
oxidizing. For the OT route (Step 10), no reducing agent will be used.
Steps 8-10Confirmatory Monitoring
These steps are similar to Step 3, but are now used to confirm the HRSG boiler water
choice. The same matrix of operating conditions and parameters should be monitored.
This will include Fe, cation conductivity, ORP, pH and TOC.
For the AVT case running in the reducing mode (Step 8), it will again be important to
confirm that severe reducing conditions do not exist in the LP HRSG evaporator circuit
due to concentrating reducing agent.
At this stage, each drum pressure HRSG circuit should be operating with the optimum
treatment. There should be a developed set of guidelines for the chemical control of the
drum HRSG; the details for this are included in the chemistry sections for AVT (Section
4.7) and OT (Section 7.3).
Obviously if the operating conditions become unsatisfactory in any way, it would be
necessary to return to Steps 8, 9 or 10.
Step 12Commissioning or Operation with Non-Volatile Treatment
This route is followed if the initial commissioning and operation of the HRSG circuit on
volatile treatment (Steps 2 and 3) indicates one or more problems; or if the initial
operation of the HRSG circuit was with a non-volatile treatment.
It is strongly suggested that the PT chemistry is the initial choice.
9-19

Step 13Baseline Review and Monitoring

This step is reached by two routes. The first is because initial operation on volatile
treatment has indicated possible problems (Steps 2-4). The second route relates to if the
HRSG has already been operating for some time with a phosphate treatment (maybe
CPT, EPT or PT). As in Step 3 it is necessary to initially review the current phosphate
treatment to determine whether it is optimum.
This initial review involves operating experience with the current phosphate treatment,
and particularly determining whether phosphate hideout and return occurs, and
whether excessive sodium phosphate carryover occurs.
Do phosphate hideout and return occur, together with any pH instability during
transients, shutdown and startup?
Has the HRSG experienced any tube failures in the last five years, and have any of
these been waterside related? Here the relevant failure mechanisms are hydrogen
damage, caustic gouging, acid phosphate corrosion, or corrosion fatigue (see Section
1.10 and 9.1).
Have any deposits been observed in the steam turbine? If phosphate deposits have
been found, then HRSG drum level control and boiler carryover problems might
exist, which need to be addressed prior to converting to EPT or CT.
Have serious condenser in-leakage and makeup water contaminant excursions

occurred?
phosphate treatment is not providing adequate chemical control, then it is suggested
that the other road map steps (14-23) should be followed.
If these reviews and those in Step 1 indicate problems or potential problems, then the
baseline monitoring will provide the key direction and should involve as complete a
program as possible, which will not only quantify the chemistry parameters, but will
also address the flue-gas side conditions and the unit flow-, and hydro-dynamics.
This program will utilize the installed chemistry monitoring systems, the core
parameters (Table 2-1), supplemented by monitoring and some of the parameters under
Additional Monitoring or Diagnostic Parameters in the same table.
Varying Operating Conditionsbase load, startup, shutdown, cycling
9-20

HRSG Boiler Water Chemistry with Blowdown Open and Closedsodium,

phosphate, free sodium hydroxide, chloride, sulfate, silica, pH, cation conductivity,
Fe, Cu, and carryover
Steam Chemistrycation conductivity, sodium (as a measure of both salts and free
hydroxide), phosphate, chloride, silica, sulfate, and boiler carryover of these
chemicals

products (Fe, Cu), oxygen, pH, and oxidizing-reducing potential (ORP)
Operation of Condensate Polishers (if included in cycle)
by monitoring total carryover (Section 2.6). Concern must also be given to any
contaminants introduced to the steam by way of the feedwater used for temperature
control (attemperation).
For the feedwater, there is a need to review the reducing agent usage. For all-ferrous
feedwater systems, the feedwater should be monitored with and without hydrazine
additives or other reducing agent alternatives. For units that continue to use a reducing
agent after optimizing the feedwater (Section 9.4), it is important to monitor the
concentration of the reducing agent or the oxidizing-reducing potential (ORP) in the LP
HRSG evaporator circuit. In HRSG units treated with AVT, the reducing agent has
been found to reach very high levels (100s of ppb) compared with normal feedwater
levels, and can give rise to very reducing HRSG boiler water conditions (ORP around
350 mV or lower). This may be an indicator that FAC is possible in the LP circuit.
Organics (natural, from amines, and from condensate returns) should also be checked
as these can also be very high in LP evaporator circuits. TOC should be less than 200
ppb.
The circulation ratio of the boiler should be determined to assess the likelihood of
deposition and/or dryout; this is an extremely important prerequisite for the
application of CT and is referred to again in Steps 21 and 22. The flue gas temperature
entering the particular pressure section should be determined as stratification of flue
gas can often vary by over 100C in each pressure section, which could be exacerbating
FAC, deposition problems, and dryout.
Step 14Assessment of Feedwater/Condensate Contamination Frequency
The review and baseline monitoring (Step 13) should indicate the likelihood and
frequency of cycle contamination events. One way of doing this is to determine how
closely the unit has met the guideline limits for feedwater, and the amount of time, in
9-21

the past (2-3 years), that the unit has been out of normal target limits. For example, an
operator might want to consider the cumulative hours equivalent to Level 1 for
economizer inlet cation conductivity as being acceptable and controllable
contamination. Excursions to more serious levels (2, 3 and even shutdown) should also
be assessed.
Step 15Consider/Convert to EPT
Consider converting to, or optimizing EPT if the feedwater contaminant events are not
considered to be significant, the condenser is tight or has titanium tubes, and the
cooling water is fresh. It is very important with EPT to note the very restrictive
chloride HRSG boiler water limits, which are required to avoid possible hydrogen
damage failures. Thus the importance of Step 14 for EPT.
The necessary detailed guidance for EPT is included in Section 3.7. The equilibrium
level should be developed (Figure 3-19) and only tri-sodium phosphate and sodium
hydroxide additions should be made.
Step 16Confirmatory Monitoring
This step is similar to Step 13, but is now used to confirm the HRSG boiler water EPT
choice. The same matrix of operating parameters should be monitored. Here it is
necessary to determine that the equilibrium level can be maintained, and if hideout and
hideout return occur.
It is important to monitor carryover and especially sodium.
If the non-volatile route has been followed because Step 3 indicated a possibility of
FAC in the LP HRSG evaporator tubing, then it is important in this step that the
monitoring confirms that FAC has been reduced.
Steps 17 and 18Cooling Water Sources
If Step 14 indicates that there is a possibility that frequent contaminant events could
occur, then consideration has to be given to the cooling source: fresh water, saline
water, or cooling towers.
Steps 19 and 20Consider/Convert to PT or CT
The necessary detailed guidance for PT and CT is included in Sections 3 and 6. The
choice is essentially an individual operators choice, although CT will provide slightly
greater protection against contamination ingress, especially chloride, and was
9-22

originally designed for this eventuality. However, some operators have a fear of
caustic gouging in HRSG tubing, and of carryover into the steam circuits. These
features are usually contrasted with the possibility of hideout, hideout return, and
more difficult control with PT. Thus the confirmatory monitoring in Step 21 is essential
for either treatment.
Step 21Confirmatory Monitoring
This step is similar to Step 16 for EPT and the initial baseline monitoring, Step 13, and
is now used to confirm the HRSG boiler water PT or CT choice. The same matrix of
operating parameters should be monitored.
For CT particular concern should be given again to carryover and especially of sodium.
See steam limits in Section 6.3. Dryout is also extremely important as it could result in
caustic gouging in the higher pressure circuits. Thus there is a need to review the
fireside and hydrodynamic monitoring discussed in Step 13.
For PT (using only tri-sodium phosphate additions), hideout and hideout return are of
concern from an operating viewpoint. Carryover of sodium is important also.
Step 22Outcome of Step 21
If with CT, the results of Step 21 indicate dryout and/or carryover, then this may
suggest that CT is not the optimum choice and PT should be used.
At this stage, each drum pressure HRSG circuit should be operating with the optimum
treatment. There should be a developed set of guidelines for the chemical control of the
drum HRSG; the details of this are included in the chemistry sections for EPT and PT
(Section 3) and CT (Section 6).
Obviously if the operating conditions become unsatisfactory in any way, it would be
necessary to return to Steps 16 or 21.
Considerations for Multiple Pressure Drum Cycles

In parallel to the selection of the chemistry for individual HRSG drum pressure circuits,
as outlined in the previous road map subsection, the various possible interactions
between circuits may need to be considered.
9-23

Section 1.11 indicated that due to the existence of so many HRSG system designs, it is
impractical to develop, in a guideline format, a comprehensive discussion which can
cover each unique configuration. Thus the operator will need to be cognizant of the
differences, which exist between the cycles (Figures 1-16 and 1-17) represented in the
cycle diagrams in this guideline and what are actually in the plant. Some of these
which will influence the chemistry choice are:
IP and HP circuits may be fed from the LP circuit.
HP circuits may be fed from the IP circuit.
Cascade blowdown may be practiced on multiple pressure drum HRSGs.
Attemperation water may be taken from the LP circuit or the feedwater circuit.
HRSGs may have a reheater.
Deaeration may be performed from the feedwater system or from the LP circuit.
Feedwater heaters/preheaters may or may not be included.
Condensers may be water or air cooled.
Condensate polishers may or may not be included.
9.6 REFERENCES
1. PWR Advanced All-Volatile Treatment Additives, By-Products, and Boric Acid, Electric
Power Research Institute, Palo Alto, Calif., TR-100755, Final Report, July 1992.
2. Workshop on Use of Amines in Conditioning Steam/Water Circuits, EPRI, Tampa,
Florida, September 25-27, 1990
3. VGB Conference, Organische Konditionierungs-und Sauerstoffbindemittel,
Lahnstein, Germany, March 1994.
4. R. B. Dooley, J. Mathews, R. Pate and J. Taylor, Optimum Chemistry for AllFerrous Feedwater Systems: Why Use an Oxygen Scavenger?, Proc. 55th
International Water Conference, Pittsburgh, PA, Oct 1-Nov 2, 1994.
5. Cycle Chemistry Guidelines for Fossil Plants: All-Volatile Treatment, Electric Power
6. Cycle Chemistry Corrosion and Deposition: Correction, Prevention, and Control, Electric
Power Research Institute, Palo Alto, Calif., TR-103038, December 1993.
9-24

7. Monitoring Cycle Water Chemistry in Fossil PlantsVolumes 1-3, Electric Power

Research Institute, Palo Alto, Calif., GS-7556, 1991/2.
9-25
10
SHUTDOWN AND LAYUP CONSIDERATIONS FOR
COMBINED CYCLE/HRSG SYSTEMS
10.1 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:
turbine blade and disk pitting;
boiler drum and tube, feedwater heater(if utilized), and condenser pitting and
oxidation; and
stress corrosion of condenser and feedwater heater (if utilized) 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, for this purpose.
Preventative measures for protecting steam cycle equipment during shutdown for
inactive periods, including short-term and longterm layup, are presented in this
section.
The practices outlined in this section are the best practices used for conventional fossil
plants. There is currently not an enormous data base for shutdown and layup for
HRSG/combined cycle units, so the procedures may need to be customized.
10-1

Shutdown and Layup Considerations for Combined Cycle/HRSG Systems
10.2 LAYUP PRACTICES

The procedures for layup of idle equipment fall into two general categories: wet and
dry methods. In general, with the exception for units on OT, wet layup requires filling
of most of the system with an alkaline reducing solution 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 HRSG and its related equipment, one should consider
the following(1):
the compatibility between the chemistry required for layup and that used during
operation;
the possibility the HRSG 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
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 10-1 (18).
10-2

Table 10-1
Shutdown and Layup Alternatives Showing Advantages and Disadvantages for Each
Alternative
Advantages
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
Disadvantages
1. Possible contamination of some circuits
when draining
2. Need to recirculate
highly concentrated
layup solutions
regularly
3. Hydrazine possible
carcinogen
4. High water
consumption prior to
startup; solution must
be drained and
possibly rinsed
5. Regular monitoring
6. 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
(demineralized) must
be used
11. Waste/environment
concerns
12. Superheaters/Reheaters and steam lines
need careful analysis.
_______
*Requires nitrogen
blanket.
10-3

Advantages
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
Dry air
Disadvantages
1. Very dangerous;
asphyxiation of
workers if not
properly vented
2. Preferably to be
carried out while
system is being
drained
1. Readily available basic

constituent
1. Drying equipment
and blowers required
2. Maintenance on plant
performed without
problems
2. Climatic conditions
may cause rapid
deterioration in
storage conditions
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
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
9. Power consumption
10. Large connections to
pressure parts.
10-4

Short-term vs. Longterm Layup

Current layup practices vary widely, from the protection of all cycle components
during longterm boiler 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 for conventional fossil plants:
Maintain condenser vacuum and turbine seals to protect the condensate system
from air ingress.
Provide auxiliary steam to blanket the deaerator (if utilized). If auxiliary steam is
unavailable, pegging steam from an adjacent unit or from the drum should be
provided. For longer outages, or in the absence of available steam, nitrogen
blanketing may be more convenient.
Nitrogen or steam blanket the HRSG boiler. The nitrogen or steam inerting systems
should be automatic with multiple injection points on the boiler, deaerator,
superheater and feedtrain vents. An automatic system is preferred to ensure a fast
(10)
response on units undergoing frequent shutdowns .
Successful extended boiler layups have been accomplished using one of the following
options:
Wet layup with a pH of 10.0 achieved with ammonia, and up to 200 ppm of
hydrazine(11), and condensate-quality water plus a pressurized nitrogen blanket.
(Note: The use of hydrazine is not recommended for units on oxygenated treatment.
Refer to Sections 7 and 8 for recommendations for OT units.) High concentrations of
ammonia should be prevented from coming into contact with copper alloys.
Wet layup with treated good-quality boiler water of the same chemical composition
as that used during operation; or
Dry layup in which a hot boiler is drained and purged with nitrogen or
dehumidified air.
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.
To use this procedure on HRSG/combined cycles, the individual boiler design must be
carefully considered when determining the number and location of nitrogen feed
10-5

points: no HRSG boiler part at any time should be exposed to vacuum. However, it is
clear that one feed point will not be sufficient.
10.3 WET LAYUP

Wet layup is a popular method of protecting a conventional fossil plant unit when it
might have to be returned to service on relatively short notice(13). It generally involves
filling the unit with treated water containing an excess of an oxygen scavenger.
Depending on design, the oxygen scavenger may be eliminated assuming a viable
nitrogen blanketing system is available(12). 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 is generally recommended
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(14) using a bulk nitrogen system comprised of liquid
nitrogen storage and provided with evaporators to convert the liquid nitrogen to gas.
A nitrogen cap:
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 have been utilized on conventional plants with a bulk
nitrogen system(14):
Main Condenser and Turbine
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
Nitrogen is added when the deaerator is still hot
10-6

Nitrogen is purged for about 20 minutes followed by the maintenance of a small

nitrogen positive flow
Feedwater Heaters (if utilized)
Nitrogen is supplied through a shell-side vent line
Steam Drum
Nitrogen enters the drum through vent lines
Nitrogen feed is started while the drum is still hot
During wet layup, the oxygen scavenger concentration should be monitored. Also, the
boiler and economizer 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.
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.
10.4 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 on conventional plants, and is
gaining in popularity 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 10-1, 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. It is suggested that
relative humidity levels of 40% or less are used to provide a reasonable margin. It is
also important that maximum effort should be given to ensuring that there are no pools
or areas of free water, otherwise pitting is a possibility.
10-7

Corrosion Rate
A desiccant dehumidifier commonly used for layup of conventional boilers and

auxiliaries, is shown in Figure 10-2(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.
20
40
60
Humidity of the air (percent)
Figure 10-1
Corrosion rate of steel relative to humidity of air
10-8
80
100

Wet air
outlet
Reactivation air
inlet filter
Dry air outlet
Reactivation
fan
Reactivation
air heater
Desiccant wheel
Reactivation
sector
Humid air
inlet filter
Dry air fan
Figure 10-2
Rotary desiccant dehumidifier(17)
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
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:
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.
10-9

The system utilized to supply dry air to the various components of the feedwater,
steam and boiler circuits must be customized to adapt to various heat cycle
configurations. To illustrate the procedure, Figure 10-3 provides an example from a
conventional fossil plant. The flow path for Figure 10-3 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. Dry air passes from
the hotwell through the condensate pumps and returns to the DH via 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.
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 10-3
Steamside Dehumidification Flow
Air moisture levels are 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%.)
10-10

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 through small leaks, which could lead to
corrosive acids and salts; which could happen if maintenance work is being undertaken
on the steam or water tubes of the HRSG.
Another customization approach(20) 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 10-2) capable of delivering a
maximum flow of 2250 scfm (3820 sm3/h) 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 blading 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 needs to be 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).
10.5 PREHEATERS, FEEDWATER HEATERS, CONDENSER, REHEATER

AND STEAM TURBINES
When developing a procedure for shutdown and layup of HRSG/combined cycle
plants, particular care must be exercised not only for the HRSG boiler proper, but also
10-11

for the remaining components of the heat cycle. Some considerations for the remainder
of these components follow.
These components are generally considered as a group, since they cannot be isolated
without special facilities being incorporated. In conventional plants, these components
are generally stored dry.
Steam Turbine
An example of dry layup of a turbine in a conventional plant is shown in Figure 10-4(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 another turbine, Figure 10-5 shows the values of temperature
and air humidity when using two air dehumidifiers (1 with 1.1 kW and 1 with 5.4 kW).
Turbine dry layup using dehumidified air can also be combined with dry layup of the
unit steamside circuits. Figures 10-3 shows an example.
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
Figure 10-4
Turbine: Dry Layup Using Dehumidified Air(23)
10-12
Manhole
Closed

35.5/18.2C
f = 16%
37.0/18.3
f = 14%
H.P.
I.P.
48.8/20.8C
f = 5%
LP
21.2/10.8C
f = 25%
56.5/22.1C
f = 2%
Air drier
1.1 kW
29.7/18.5C
f = 35%
30.7/16.0C
f = 20%
Air drier
5.4 kW
23.8/16.5C
f = 47%
18.2/10.2C
f = 33%
18.3/10.2C
f = 33%
Figure 10-5
Dry Layup of 107 MW Turbine Showing Measured Values of Temperature and Air
Humidity
Preheater/Feedwater Side of Condensers and Preheater/Feedwater Heaters (if

utilized)
The metallurgy of these components must be carefully considered when establishing
the feedwater chemistry for intermediate or long term storage. A recent EPRI
publication(15) 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).
Superheater
If the superheater is stored wet, then it should be back filled with treated water of a
composition identical to that used for the boiler. A nitrogen cap should be used to
prevent air ingress.
Deaerator and Storage Tank

The deaerator and deaerator storage tank should be protected by a steady, small
nitrogen purge.
10-13

10.6 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.
10.7 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
and 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 conventional 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,
but could be a few hours to a day). 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 HRSG water.
When the boiler decays to 5 psi (0.03 MPa) pressure (typically 7 days, but could be as
short as 1-2 days) a nitrogen cap is applied to the HRSG steam drums.
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.
10.8 REFERENCES
1. The ASME Handbook on Water Technology for Thermal Power Systems. American
Society of Mechanical Engineers, New York, NY 1989.
10-14

2. VGB Guidelines. Preservation of Power Plant Systems. VGB-R116H. VGB

Technische Vereinigung 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.
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
th
10 , 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.
10-15

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.
10-16
A
MANUFACTURER'S HRSG CHEMISTRY GUIDELINES
Siemens Recommendations for the Chemical Treatment of the Steam Water

Cycle of HRSGs
The preferred water treatment is AVT. An elevated pH in feedwater of > 9.8 by dosing
of ammonia minimizes the risk of FAC in the LP evaporator. A dosing system for solid
alkalizing agent is provided for cases of malfunction.
The target value for oxygen in the feedwater is < 100 ppb at cation conductivities < 0.2
S/cm. Cation conductivities > 0.2 S/cm require an oxygen concentration < 20 ppb.
A-1

Manufacturer's HRSG Chemistry Guidelines
A-2

A-3

A-4

A-5

A-6

A-7

A-8

A-9

ALSTOM ENERGY SYSTEMS

HRSG FEED WATER & BOILER WATER GUIDELINES
FEED WATER
cation conductivity at 25C

target value
< 0.3 S/cm

0.2 S/cm
pH at 25C
9.2 to 9.6
dissolved oxygen at deaerator outlet
< 0.007 ppm
total silica (as SiO2 )
< 0.02 ppm
hydrazine excess at economizer inlet
0.01 ppm
total iron (as Fe)
< 0.02 ppm
total copper (as Cu)

1
2
For feed systems copper free.

Hydrazine is injected at condensate pumps outlet. Hydrazine is ruled out in
some cases
For feed systems which include copper alloys, pH 9.0 0.2
BOILER WATER
Pressure psig
85 - 570
cation conductivity at 25C
NA
< 3 S/cm
NA
specific conductivity at 25C
< 50 S/cm
< 5 S/cm
< 20 S/cm
pH at 25C
9.2 to 9.7
9.0 to 9.2
9.0 to 9.7
phosphate (as PO4 )
3 to 5 ppm
no
< 3 ppm
silica (as SiO2 )
< 5 ppm
< 0.8 ppm
< 0.8 ppm
not detectable
not detectable
not detectable
chlorides (as Cl )
IP.LP.BOILER WATER
PT
specific conductivity at 25C
< 50 S/cm
pH at 25C
9.2 to 9.7
phosphate (as PO4 )
3 to 5 ppm
silica (as SiO2 )
< 5 ppm
chlorides (as Cl )
A-10
< 0.005 ppm
not detectable
1070 - 2000

Interim Cycle Chemistry Guidelines For Combined Cycle Heat Recovery Steam Generators (HRSGS) - TR-110051

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Interim Cycle Chemistry Guidelines

for Combined Cycle Heat Recovery

Final Report, November 1998

EPRI Project Manager

DISCLAIMER OF WARRANTIES AND LIMITATION OF LIABILITIES

EPRI Licensed Material

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

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1.10 HRSG TUBE FAILURES.......................................................................................... 1-26

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2.7 RATIONALE FOR TARGET VALUES OF INDIVIDUAL PARAMETERS .................... 2-29

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Target Values for HRSGs With Reheat on EPT ............................................................ 3-25

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Hot Start.......................................................................................................................... 5-9

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Chemical Dosing ............................................................................................................. 8-9

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Preheater/Feedwater Side of Condensers and Preheater/Feedwater Heaters (if

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Figure 2-2 Schematic of Operating Ranges of Boiler Water on Equilibrium Phosphate

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diagrams for once-through HRSG units. Operators should apply the

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1.1 BRIEF HISTORY

Heat Rate, Btu/kWh (J/Wh)

Simple gas turbine

Gas turbine plus unfired single

Advanced gas turbine plus

Gas turbine plus dual pressure

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quick response peaking service capability

low operating costs (manpower, fuel)

reduced emission of greenhouse effect gases such as CO2

1.2 TYPES OF CYCLES AND STEAM GENERATORS

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25,000 to 5,000,000 lb/h (0.32 to 630 kg/s)

Gas turbine outlet temperature

Supplemental firing temperature

15,000 to 1,000,000 lb/h (1.9 to 127 kg/s)

2000 psig (138 bar)

50 to 400 psig (3.4 to 28 bar gauge)

15 to 50 psig (1.03 to 3.4 bar gauge)

#2 oil, natural gas

*Higher capacity gas turbines are now available and in use.

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Superheater approach, TSH

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Flu gas to stack

H.P. boiler feed

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