e-PPChem 2012, 14 (5) 5

PPCHEM
The International Edition
POWER PLANT CHEMISTRY
The Journal of All Power Plant Chemistry Areas
May 2012
Fossil Cycle Chemistry

EPRI Assessment of Amines
in Power Plant Chemistry

Applications
2800Si Autom
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A Practical Guide to
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The Application of High AVT(O)
in Gas Turbine Combined Cycle

Plants
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Conferences
Proceedings of the BIAPWS
2012 Symposium on Power

Plant Chemistry

The Long Road from Potatoes and Wood Shavings to Combined Amine Mixtures
Events
ISSN 1438-5325
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Visit us at http://www.ppchem.net
Volume 14 (2012) No. 5
Visit IAPWS at
http://iapws.org/
The International Association for the Properties

of Water and Steam
and download IAPWS Releases, Guidelines, and Other Documents.
For example:
Release on Ionization Constant of H2O (2007)
Guideline on the Henry's Constant and Vapor-Liquid Distribution Constant for Gases in H2O
and D2O at High Temperatures (2004)
Technical Guidance Document
"Instrumentation for Monitoring and Control of Cycle Chemistry for Steam-Water Circuits
of Fossil-Fired and Combined-Cycle Power Plants" (2009)
"Procedures for the Measurement of Carryover of Boiler Water into Steam" (2008)
"Volatile Treatments for the Steam-Water Circuits of Fossil and Combined Cycle/HRSG
Power Plants" (2010)
"Phosphate and NaOH Treatments for the Steam-Water Circuits of Drum Boilers of Fossil
and Combined Cycle/HRSG Power Plants"
IAPWS
is an international non-profit association of national organizations concerned with the properties of water and steam, particularly thermophysical properties and other aspects of hightemperature steam, water and aqueous mixtures that are relevant to thermal power cycles
and other industrial applications. IAPWS objectives are
To provide internationally accepted formulations for the properties of light and heavy steam,
water and selected aqueous solutions for scientific and industrial applications
To define research needs and promote and coordinate research on steam, water and
selected aqueous systems important in thermal power cycles
To collect and evaluate the resulting data, and to communicate and promulgate the
findings
To provide an international forum for exchange of experiences, ideas and results of
research on high-temperature aqueous media
PPCHEM
POWERPLANT CHEMISTRY
ISSN 1438-5325
Single issue price: 16.00 (+ postage and VAT).
Contents
May 2012
Editor's Comments
267

EPRI Assessment of Amines in Power Plant Chemistry Applications
268
James A. Mathews
Condensate Polishing
A Practical Guide to Investigating Operating Problems on In-situ Regenerated Polishing
Mixed Beds
282
Brian Windsor and David Hayhurst

The Application of High AVT(O) in Gas Turbine Combined Cycle Plants
288
Takashi Suzuki, Tetsuo Yamamoto, Masanobu Maekawa, Jun Hishida, Satoshi Kuwano,
and Kazumitsu Takanishi
Conferences
Proceedings of the BIAPWS 2012 Symposium on Power Plant Chemistry
298
Paul McCann and Mark Robson

312
Albert Bursik
Events
266, 275, 276, 306, 322
Imprint
328
New METTLER TOLEDO Thornton Silica Analyzer
2800Si Autom
Automated
mated Silica Analy
Analyzer
yzer
Protects TTurbine
urbine Int
Integrity
tegrity
g y
s Automatic, unattended calib
calibration
bration
provides repeatability
repeatability,
y,, saves
saves time
s Large reagent containers ex
extend
xtend
maintenance interval
s Full enclosure protects ana
analyzer
lyzer
and reagent containers with
without
hout
panel cutout
www.mt.com/pro
www
.mt.com/pro
The new METTLER TOLEDO Thornton 2800Si Silica Analyzer is a reliable on-line instrument
designed specifically for pure water treatment and power cycle chemistry monitoring. This
Analyzer provides assurance of water purity to optimize ion exchange production of pure
water and to minimize silica deposition in turbines. Early detection of trace contamination is
enabled with minimal operator supervision.
Applications
Ultrapure water monitoring at ppb silica levels can assure delivery of highest quality
water. Silica breakthrough of polisher anion resin is detected at very low ppb levels and
contaminated water can be diverted before it reaches critical areas.
Power steam quality monitoring protects turbines from silica deposition and resulting
imbalance, loss of capacity and efficiency. Silica measurement and control may also be
needed to meet turbine manufacturer warranty requirements.
Power condensate polisher monitoring can detect the need for regeneration at low ppb
levels before feedwater is significantly contaminated.
METTLER TOLEDO Thornton offers a full complement of pure water measurements including
conductivity, pH, ORP, dissolved oxygen, sodium, silica, TOC.
More information visit www.mt.com/pro_power
PowerPlant Chemistry 2012, 14(5)
265
PPCHEM
Events Calendar
Events Calendar
Date
PowerPlant Chemistry wants to inform you of all power plant chemistry-related conferences and other events taking place worldwide. Please help us to make our EVENTS CALENDAR more complete. Send us information on planned events by e-mail to
editor@ppchem.net. We will include it in the next version of our EVENTS CALENDAR. Your cooperation is much appreciated.
Venue
Event
Information
May 2123, 2012
Holiday Inn Hotel

Heidelberg, Germany
Third International Conference Interaction of Organics and

Organic Cycle Treatment Chemicals with Water, Steam, and
Materials
http://www.ppchem.net
May 2124, 2012
Penta Hotel
Leipzig, Germany
5th International Freiberg Conference on IGCC & XtL

Technologies
http://www.gasification-freiberg.org/
desktopdefault.aspx/tabid-16
May 2124, 2012
Hyatt Regency Bellevue on Seattle's

Eastside
Bellevue, WA, U.S.A.
9th International Conference on Nondestructive Evaluation in

Relation to Structural Integrity for Nuclear and Pressurized
Components
http://www.cvent.com/EVENTS/Info/Summary.aspx?e=
92014b50-15bd-45fc-a48d-7f80b4e6bc88
May 2324, 2012
Novotel Krakw Bronowice

Krakw, Poland
VGB Workshop "Flue Gas Cleaning 2012"
http://www.vgb.org/en/flue_gas_cleaning_2012.html
May 2730, 2012
The Crowne Plaza Terrigal

Terrigal, NSW, Australia
API PowerChem Conference
http://www.tmm.com.au/whats-coming-up/details/
62-Powerchem2012.html
June 57, 2012
Hawthorn Suites by Wyndham

Champaign, IL, U.S.A.
32nd Annual Electric Utility Chemistry Workshop
http://www.conferences.uiuc.edu/conferences/conferen
ceviewer2/view.cfm?conf=20041
June 1819, 2012
Centro Congressi Fast

Milano, Italy
Solid Particle & Liquid Droplet Erosion: Testing, Modeling, and

Applications
http://www.cvent.com/events/solid-particle-liquiddroplet-erosion-testing-modeling-and-applications/
event-summary-913d8fce4fdd41b28a2d4fbfba9da
46c.aspx
June 1921, 2012
Loews Ventana Canyon

Tucson, AZ, U.S.A.
International Low-Level Waste Conference and Exhibition 2012 http://www.cvent.com/events/international-low-level

-waste-conference-and-exhibition-2012/event-summ
ary-2b986f2376924a7a947ae867d48b244e.aspx
June 2429, 2012
The University of Colorado

Boulder, CO, U.S.A.
18th Symposium on Thermophysical Properties
http://www.thermosymposium.boulder.nist.gov/
June 2628, 2012
Hyatt Olive 8
Seattle, WA, U.S.A.
International Conference on Cycle Chemistry in Fossil and

Combined Cycle Plants
http://www.cvent.com/events/international-confer
ence-on-cycle-chemistry-in-fossil-and-combined-cyc
le-plants/event-summary-9d2f7ca3c522490c9e1d40
c27e3e8536.aspx
June 2729, 2012
Renaissance Orlando at SeaWorld

Orlando, FL, U.S.A.
EPRI Groundwater Protection Workshop in Collaboration with

Nuclear Energy Institute
http://www.cvent.com/events/epri-groundwaterprotection-workshop-in-collaboration-with-nuclearenergy-institute/event-summary-f38afa65291648e6879
a29ad92f016f1.aspx
July 1619, 2012
Gaylord Resort and Convention

Center
National Harbor, MD, U.S.A.
International Boiling Water Reactor and Pressurized Water

Reactor Materials Reliability Program Conference and
Exhibition 2012
http://www.cvent.com/events/international-boiling-wa
ter-reactor-and-pressurized-water-reactor-materials-re
liability-program-conf/event-summary-c36b77a9f82841
db966fd24 f181b320b.aspx
September 1113, 2012 Grand Hyatt Atlanta

Atlanta, GA, U.S.A.
Steam Generator Secondary Side Management Conference

2012
http://www.cvent.com/events/steam-generatorsecondary-side-management-conference-2012/eventsummary-c65c2f1761be4fd9960d91c557da1bd1.aspx
September 1921, 2012 Queen's College

Cambridge, United Kingdom
IEX 2012, Developments and Applications of Ion Exchange
http://www.soci.org/Membership-and-Networks/
Technical-Groups/Separation-Science-and-Techno
logy-Group/IEX-2012
September 2327, 2012 Queen Elizabeth II Conference Centre

London, England
Euromembrane 2012
http://www.euromembrane2012.com/index.html
September 2428, 2012 Paris Tour Eiffel Novotel Convention

Center
Paris, France
International Conference on Water Chemistry of Nuclear

Reactor Systems
https://www.sfen.fr/NPC-2012
September 2527, 2012 Thessaloniki, Greece
EUROCOALASH
http://www.eurocoalash.org/index.php?id=17&lng=2&t=5
October 1012, 2012
Congress Center Rosengarten

Mannheim, Germany
VGB Congress "POWER PLANTS 2012"
http://www.vgb.org/en/hv_2012.html
October 1518, 2012
David L. Lawrence Convention Center The Twenty-Ninth Annual Pittsburgh Coal Conference
Pittsburgh, PA, U.S.A.
http://www.engineering.pitt.edu/Coal_Conference/2011
_Conference.aspx
October 2425, 2012
CCH-Congress Center
Hamburg, Germany
VGB Conference "Chemistry in Power Plants 2012"
http://www.vgb.org/en/cik_2012_e.html
November 48, 2012
San Antonio, TX, U.S.A.
2012 International Water Conference
http://www.eswp.com/water/
November 78, 2012
Eurogress Aachen, Aachen, Germany
Aachener Membrane Colloquium
http://www.amk.rwth-aachen.de/
March 1721, 2013
Orlando, FL,
U.S.A.
NACE Corrosion 2013 Conference & Expo
http://events.nace.org/conferences/c2013/callforpap
ers.asp
March 2629, 2013
Westin Arlington Gateway

Arlington, VA, U.S.A.
2013 Fossil FAC International Conference
http://www.regonline.com/builder/site/Default.aspx?
EventID=1045954
September 15, 2013
Estoril Congress Center

Estoril, Portugal
EUROCORR 2013
http://www.eurocorr2013.org/
October 2224, 2013
Wiesbaden, Germany
FILTECH 2013
http://www.filtech.de/
October 2225, 2013
Hilton Waikoloa Village

Waikoloa, HI, U.S.A.
7th International Conference on Advances in Materials

Technology for Fossil Power Plants
http://www.cvent.com/events/7th-international-conferen
ce-on-advances-in-materials-technology-for-fossil-pow
er-plants/event-summary-f86961e02e7046f292622f403
df9f045.aspx
November 1721, 2013
Orlando, FL, U.S.A.
2013 International Water Conference
http://www.eswp.com/water/index.htm
266
Editor's Comments
Editor's Comments
PPCHEM
May 2012
Dear readers:
A paper authored by James A. Mathews is the first paper in this journal issue. For the first time, the Electric Power Research
Institute's results of assessments of amines for use in fossil power plant chemistry applications are presented in the open
literature. The author states that while there still remains no quantifiable evidence that the breakdown products directly
contribute to power plant damage, research has implicated organic acids involvement in stress corrosion cracking, and
equipment suppliers are reluctant to accept exceeding limits of cation conductivity from the accumulation of these
by-products. The focus of the paper is on the use of neutralizing amines in connection with two-phase flow-accelerated
corrosion, steam-side corrosion in air-cooled condensers, and processes in the phase transition zone in steam turbines. By
the way, this paper will be presented at the Third International Conference "Interaction of Organics and Organic Cycle
Treatment Chemicals with Water, Steam, and Materials" taking place in a few days in Heidelberg, Germany (EPRI
Assessment of Amines in Power Plant Chemistry Applications).
The second paper will surely be appreciated by all those operating or taking care of the operation of polishing mixed beds.
Brian Windsor and David Hayhurst give advice for troubleshooting mixed bed problems such as poor mixed bed
performance, poor resin separation, inadequate slow displacement rinsing, poor drain control prior to resin remixing, and
air blower failures. Although the paper is tailored to in-situ regenerated mixed beds, many of the points raised also apply to
external regenerated units (A Practical Guide to Investigating Operating Problems on In-situ Regenerated Polishing
Mixed Beds).
The next paper comes from Japan. Takashi Suzuki, Tetsuo Yamamoto, Masanobu Maekawa, Jun Hishida, Satoshi Kuwano,
and Kazumitsu Takanishi report on the application of a modified all-volatile treatment (AVT), high AVT(O), to 11 units with
heat recovery steam generators with a total output of 3 442 MW. This treatment eliminates the need for hydrazine injection
and ensures that the feedwater meets the quality control criteria even during plant startup/shutdown. We discussed
internally whether the term "high AVT(O)" should be used in the paper (as applied by the authors) or whether it should be
changed to "high-pH AVT(O)," which would be more informative and precise regarding the treatment conditions. Finally, we
stuck with the authors' designation since it is used in their country and was already applied in a paper published in our journal in the 10th issue in 2011 (The Application of High AVT(O) in Gas Turbine Combined Cycle Plants).
The British and Irish Association for the Properties of Water and Steam held its annual Symposium on Power Plant Chemistry
on 2829 March 2012 in Chilwell, Nottingham, United Kingdom. In the fourth May paper, Paul McCann and Mark Robson
provide brief abstracts of all the papers presented in the symposium sessions Power Plant Chemistry Fundamentals, Boiler
Chemical Cleaning, Environmental and Water Treatment Issues, and Power Plant Chemistry and Corrosion (Proceedings of
the BIAPWS 2012 Symposium on Power Plant Chemistry).
The last paper is a historical overview of the development und use of organic plant cycle treatment chemicals from the use
of potatoes, wood shavings, flaxseed, tannin, alginates (created from algae), corn and potato starch, and colloidal graphite
in the early 1900s to the modern multicomponent additives of today. It is stated that there has not been any irrefutable
evidence that up-to-date organic plant cycle treatment chemicals and/or their breakdown products are directly involved in
boiler tube failures or steam path damage. The author, the editor of this journal, sees the biggest barrier impeding the
broader use of these chemicals in the fact that no internationally renowned fossil cycle chemistry guidelines adequately
cover the use of organic plant cycle treatment chemicals in fossil plant cycles (The Long Road from Potatoes and Wood
Shavings to Combined Amine Mixtures).
That's all. Remain true to us and do not forget: the best source of the latest information on power plant chemistry is a
subscription to our journal.
Albert Bursik, Editor
267
PPCHEM
EPRI Assessment of Amines in Power Plant Chemistry

Applications
James A. Mathews
ABSTRACT
All-volatile treatment (AVT) has become the industry standard for condensate, feedwater and steam chemistry in
electric generating power plant cycles. Ammonia is the most commonly used alkalizing chemical for pH control in
these cycles but exhibits poor dissociation and high volatility, which often result in less than adequate pH control in the
first-formed condensate and liquid fraction of two-phase water/steam environments. Neutralizing amines offer characteristics to overcome the apparent deficiencies of ammonia and are finding increased usage in nuclear power and
industrial boiler applications. EPRI investigations of the application of selected neutralizing amines have demonstrated
that the decomposition rate of the amines often results in ammonia remaining as the principal alkalizing agent as well
as an appreciable inventory of organic acids (namely formate and acetate) and carbon dioxide and only a minor or
moderate residual of the original amine. While there still remains no quantifiable evidence that the breakdown products
directly contribute to power plant damage, research has implicated organic acids involvement in stress corrosion
cracking, and equipment suppliers are reluctant to accept exceeding limits of cation conductivity from the accumulation of these by-products. Results of assessments of amines for use in power plant chemistry applications are presented with a query for more definitive scientific information on the potential corrosion risks and damage mechanisms
associated with the high levels of the decomposition by-products.
INTRODUCTION
The EPRI Cycle Chemistry Program, established in 1984,
has endeavored over the past 25 years to substantially
increase the understanding of chemistry-influenced damage and the effects of deposits on unit performance.
Availability and reliability are of paramount importance to
the overall economic performance and profitability of fossil plant unit operations. Plant assessments have shown
that deficient chemistry practices reduce the efficiency
and performance of fossil plant components in contact
with water and steam. Non-optimum chemistry conditions
can shorten the useful service life of fossil plant components, requiring that replacement projects begin sooner
than normally required [1]. Failures of high-pressure components are responsible not only for extensive damage to
power plant equipment and loss of availability, but also for
injury to personnel.
applications with some apparent success worldwide, but

little scientific data on the actual chemistries is available.
Although AVT treatment provides distinct benefits in the
control of the corrosion and deposition mechanisms, the
current treatment practices do not provide the absolute
protection required in all operating conditions and circumstances. Ammonia is a relatively weak base and exhibits
high volatility at system operating temperatures and pressures, and is extremely volatile at the low temperatures
experienced in the early condensing steam. These characteristics result in less than adequate pH control of the
first-formed condensate, and can ultimately lead to
increased rates of corrosion in condensate/feedwater systems of low-pressure (LP) HRSG preheaters and evaporators and flow-accelerated corrosion (FAC) in wet-steam
piping [2].
All-volatile treatment (AVT) has become the industry standard for condensate, feedwater and steam chemistry in
fossil plant and combined cycle heat recovery steam generator (HRSG) units. The most commonly used treatments
use ammonia (with or without a reducing agent) for pH
control. Alternative products are being used in these
Neutralizing amines perform similarly to ammonia to

reduce the solubility of metallic oxides by increasing the
pH of the condensate or feedwater. The properties of
some neutralizing amines have the potential to further
optimize the cycle chemistry by improving the pH conditions in those areas where ammonia has been shown to
2012 by Waesseri GmbH. All rights reserved.
268
frequently be inadequate to control chemistry-influenced

component damage mechanisms including but not limited
to the following:
Deaerators and feedwater heaters
flow-accelerated corrosion in wet steam
LP heat recovery steam generators
flow-accelerated corrosion in evaporators and economizers in wet steam and low pH conditions
LP turbine phase transition zones
low pH conditions in the liquid films and early condensate increasing corrosion potential
Air-cooled condensers
FAC-like corrosion in the early wet steam regions of the
entrance to condensing tubes.
The potentially beneficial properties of some amines
include lower volatility to improve distribution of the amine
to the liquid phase in low-pressure applications, and
higher basicity to improve the dissociation of the amine
and higher pH at ambient and elevated temperatures.
EPRI recently conducted several investigations on the
potential use of neutralizing amines [35].
Nuclear power plants have addressed similar concerns of
low pH in condensing steam, as 2-phase FAC has
occurred in moisture separator reheaters on nuclear pressurized water reactors (PWRs) and in boiler tubes on other
designs of nuclear plants, with the application of alternate
amines. Alternative amines are currently used for alkalizing the boiler water and for pH control in fossil and nuclear
plants in the U.S., U.K. and other countries in Europe and
elsewhere worldwide [6]. The use of alternative amines is
mainly confined to lower pressure boilers, often industrial
boilers, and to relatively low-pressure combined cycle
plants with heat recovery steam generators (HRSGs).
These plants tend to be operated by "independent" operators (rather than electric generating utilities) and many
are part of a co-generation facility associated with an
industrial plant or complex. Nevertheless, there are
instances of amine use in full-scale operating thermoelectric generating plants and HRSGs. The amines typically
are provided as proprietary chemicals, consisting of a
blend of products which may include other constituents
such as dispersants, chelants or film-forming amines in
addition to the combination of one or more alternative
"neutralizing" amines. Typically the amines most frequently used include: morpholine, cyclohexylamine,
2-aminoethanol (ethanolamine) and 3-methoxypropylamine.
Amines have been used in low-pressure/temperature
industrial power plants for many years. In these applications, the amine products have provided varying levels of
success. However, for high-pressure, high-temperature
utility plants the problem, or potential problem, of thermal
PPCHEM
decomposition of the amines to low molecular weight

organic acids and ultimately to carbon dioxide is of significant concern. The use of organic treatment chemicals,
including neutralizing and filming amines, has not been
addressed in major power plant cycle chemistry guidelines, including those produced by EPRI for fossil and
combined cycle plants. EPRI's Comprehensive Cycle
Chemistry Guidelines for Fossil Plants, published in
December 2011, took a step forward by the addition of a
short appendix section on "Neutralizing and Filming
Amines" [1].
There are many reasons for the omission of amines from
existing guidelines including the philosophy that alternative products should not be needed if the proper chemistry control in the water/steam cycle is used, the belief
that breakdown products resulting from thermal decomposition pose problems with the analytical measurement
of cation conductivity and operation of condensate polishers, and the potential corrosion concerns associated with
the breakdown products. Major equipment suppliers' concerns about the potential impact of carbon dioxide and
organic acids such as formates and acetates on stress
corrosion cracking and corrosion fatigue of turbine steels
and the increase of flow-accelerated corrosion (FAC) in
2-phase fluids have been the basis for reluctance to investigate options of amine treatments. These acids can circulate through the water/steam circuit and it is essential to
maintain alkaline conditions throughout to minimize the
risk of corrosion.
Numerous utilities worldwide report using various amines
in fossil plants, although few have reliable documented
data on the effectiveness or thermal decomposition products. For those few that have reported findings, the general conclusion is that there is a resulting increase in the
cation conductivity levels in the water/steam cycle ranging
between 0.30.7 S cm1 with some higher values
reported. Reported monitoring of ammonia concentration
has typically demonstrated a nearly complete thermal
decomposition of the amine to ammonia. The reasons for
selection of the use of the particular amine(s) are similarly
not clearly identified.
The thermal decomposition products of alternate amines
most often include ammonia, carbon dioxide, and formic
and acetic acids. Although the alkalizing effect of the
amine may counter the effects of the formation of low
molecular weight organic acids, evidence indicates that
acetates are not benign and lead to stress corrosion
cracking of steel. Acetic acid has been reported to be
found to be a deleterious species with respect to stress
corrosion cracking (SCC) of turbine steels [10].
Even if neutralized, it is still not absolutely clear whether
organic acids are without danger to the boilers, superheaters and, especially, turbines. The production of car-
269
PPCHEM
bon dioxide reduces the neutralizing capacity of the

chemicals present and increases the cation conductivity
of the steam, complicating on-line monitoring and often
causing the steam turbine manufacturers' limits to be
exceeded [11].
Organic treatment of a dual-pressure combined cycle
HRSG (0.7/62 MPa, 170/485 C) with 2025 mg kg1
(ppm) morpholine-based proprietary amine mixture and
organic oxygen scavenger exhibited high-pressure (HP)
steam cation conductivity values of 0.50 S cm1. The
boiler water was conditioned with tri-sodium phosphate
(Na3PO4) to achieve a pH of 9.7. Reported acetate concentrations were HP boiler 500 g kg1 (ppb), HP steam
30 g kg1. Cation conductivity due to carbon dioxide
(CO2) in the HP steam was reported to be 0.25 S cm1.
The volatility of acetate was demonstrated to be highly
dependent on the pH of the boiler water by raising the pH
of the HP boiler to 10.25 with a corresponding increase in
the boiler acetate levels to 720 g kg1 and a decrease of
the HP steam values to 20 g kg1. The plant has reportedly operated successfully for several years [12].
Russian once-through boilers (300, 500 and 1 200 MW)
with condensate polishing reported damage exhibiting
brittle cracks and granular stress corrosion as a result of
contamination in the feedwater with organic matter. The
cation conductivity values of the steam were typically a
factor of at least three higher than corresponding condensate and feedwater on the same unit as a result of thermal
decomposition of organic contaminants. Ammonia in the
feedwater treatment was insufficient to neutralize the carbon dioxide, and formic and acetic acid decomposition
products which were reportedly responsible for the component damage [13], however the local presence of inorganic anions in the cracks was also reported.
Three units of a Grecian plant (70, 125, 125 MW) operating
with all-volatile treatment (AVT) adapted the boiler treatment to a mixture of initially 3-methoxypropylamine and
ethanolamine and finally to a mixture of ammonia (10 %)
and ethanolamine (5 %). The amine addition was made in
response to internal corrosion of the units and to provide
additional alkalizing of the boiler water due to CO2 generation from the use of carbohydrazide reducing agent. In the
8.2 MPa (1 200 psi) and 12.2 MPa (1 800 psi) boilers, the
necessary level of ammonia could not be maintained to
achieve adequate pH control (pH 9.00.2) without
exceeding ammonia and pH limitations of the copper metallurgy in the condensate. 3-methoxypropylamine was
replaced during the evaluation to reduce the level of alkalization in the boiler and to increase the pH control levels
of the condensate. Goals of iron and copper transport
reduction and pH control of the boiler and condensate
were reasonably achieved; however from the reported
data it is unclear if the targeted 0.3 S cm1 cation conductivity of the condensate was successfully maintained,
270
and the thermal decomposition resulting from operation

with 538/538 C superheat/reheat temperatures was not
monitored. After five years no corrosion damage is
reported [14].
An investigation of alternative amines for feedwater conditioning of a mixed metallurgy 500 MW, 16.5 MPa,
538/538 C unit to lower the condensate ammonia concentration concluded that none of the alternative amines
achieved the reduction. The testing found that any of three
amines investigated (cyclohexylamine/morpholine blend,
2-(diethylamino)ethanol (diethylaminoethanol), and piperidine) is adequate for pH control of the feedwater and
steam if used at the proper concentration. Cation conductivity of extraction steam provided a relative indication of
the thermal decomposition (supported by the consumption expressed on the basis of moles of amine per unit of
feedwater treated) of each of the products:
ammonia 0.150.20 S cm1,
cyclohexylamine/morpholine blend 0.400.50 S cm1,
diethylaminoethanol 0.600.70 S cm1, and
piperidine 0.400.45 S cm1.
No data were collected to determine the actual thermal
decomposition products [15].
Similar reports of alternative amine use or investigation in
fossil plants ranging from 8.319.3 MPa have indicated no
problems directly attributable to amine use but increases
in cation conductivity were noted. Replacement of ammonia on a 19.3 MPa unit with morpholine resulted in a cation
conductivity increase to 0.4 S cm1, and a reported
40 g kg1 formate in the steam [16]. These values are in
close agreement with the expected cation conductivity
values for steam also containing 20 g kg1 CO2 according to theoretical contributions reported by Jonas [11].
Use of cyclohexylamine resulting in 0.20.3 S cm1
steam cation conductivity has been reported for a
16.5 MPa unit. Likewise, many HRSG facilities report
using proprietary blends of amine products at elevated
cation conductivities but report few if any related damage
episodes.
USE OF NEUTRALIZING AMINES

There are three distinguishing characteristics of neutralizing amines that affect their applicability in the fossil plant:
Dissociation
The degree that an amine ionizes at different pressure/
temperature conditions. The relative dissociation determines the pH at operating conditions pHT;
Distribution
The degree that an amine distributes between steam
and water in two phase conditions at different power
plant pressure/temperature conditions;
PPCHEM
Chemical
pKb
Relative
Concentration
pH
1
]
Molecular
Mass
[mmol
L
25 C 150 C 300 C
25 C 150 C 300 C
2-aminoethanol (ethanolamine, ETA)
4.8
4.5
6.4
61
0.1
9.6
7.1
6.2
3-methoxypropylamine (MPA)
4.6
4.1
6.6
89
0.1
9.8
7.2
6.1
Dimethylamine (DMA)
3.6
3.2
5.4
45
0.1
9.9
7.5
6.6
Morpholine
5.3
5.5
6.5
87
0.1
9.2
6.9
6.1
Cyclohexanamine (cyclohexylamine)
3.4
4.2
5.9
99
0.1
9.9
7.4
6.4
Ammonia
5.2
4.8
6.7
17
0.1
9.5
7.0
6.0
18
7.0
5.8
5.7
Water
Table 1:
Dissociation: base dissociation constant (pKb) for neutralizing amines and ammonia and pH of 1.0 mmol L1 solutions at 25 C (77 F),
150 C (302 F), and 300 C (572 F). Adapted from [3].
Amines with higher dissociation than ammonia will produce more alkaline conditions than possible with an
equivalent ammonia solution. Amines with lower distribution than ammonia will result in more alkaline conditions in
two-phase mixtures than possible with an equivalent
ammonia solution. These two factors are offset by the
decomposition (thermal) of amines, which will result in the
release of ammonia, organics (including acetates and formates), and carbon dioxide [1,2,11]. These decomposition
products can negate the additional alkalinity contributions
from neutralizing amines and may contribute to stress corrosion cracking or pitting of austenitic steels, including
turbine materials.
Table 1 provides the relative base dissociation constants
(pKb) at three reference temperatures for typical neutralizing amines applicable for use in fossil plants; the pKb
values for ammonia are included as reference points.
Essentially the lower the value of the pKb, the more basicity the amine possesses.
With the exception of morpholine each of the neutralizing
amines has a higher basicity on a mole per mole basis
than ammonia. Figure 1 provides the pKb across all
temperatures up to 315 C and illustrates the relative
basicity of ammonia (NH3), morpholine, dimethylamine,
3-methoxypropylamine, 2-aminoethanol (ethanolamine),
and 5-aminopentanol through the operating temperature
range.
Accordingly, morpholine is the least basic at the low end
of the temperature range and ammonia is the least basic
at the high end of the range. Dimethylamine is the most
basic across the temperature range. It is expected that the

most alkaline conditions on an equivalent molar concentration basis would be achieved with the application of
dimethylamine, and the least would be with morpholine in
the low temperature portion of the cycle and ammonia
(NH3) in the high temperature range.
Figure 2 illustrates the relative distribution of ammonia
(NH3), morpholine, dimethylamine, 3-methoxypropylamine, 2-aminoethanol (ethanolamine), and 5-aminopentanol across the fossil power plant operating temperature
regimes.
NH3
Morph
DMA
MPA
ETA
5-AP
7.0
6.0
pKb
Decomposition
The degree to which an amine decomposes into simpler organic molecules and ammonia at different pressure/temperature conditions.
5.0
4.0
3.0
37.8
93.3
148.9
204.4
260.0
315.6
Temperature [C]
Figure 1:
Effect of temperature on the base dissociation constant (pKb) of
common amines [3].
Morph
DMA
MPA
ETA
5-AP
morpholine
dimethylamine
3-methoxypropylamine
2-aminoethanol (ethanolamine)
5-aminopentanol
271
PPCHEM
NH3
Morph
DMA
MPA
ETA
5-AP
2.0
1.0
logKd
0
1.0
that the amine additions (as practiced at the sites tested)

had little effect in the two-phase regions for adjustment of
the pHT (pH at operating temperature). In some instances,
simulation results indicated that better performance would
have been realized with ammonia alone due to the presence of excess concentrations of acetate and formate
(organic acid production from thermal breakdown of neutralizing amine). Except for increasing the cation conductivity and lowering the pH, the effect of the increased
concentration of acetate and formate is not fully known.
2.0
3.0
37.8
93.3
148.9
204.4
260.0
315.6
Temperature [C]
Figure 2:
Logarithm of the distribution coefficient Kd versus temperature [3].
Morph
DMA
MPA
ETA
5-AP
morpholine
dimethylamine
3-methoxypropylamine
2-aminoethanol (ethanolamine)
5-aminopentanol
Dimethylamine is the most volatile across the temperature

range and 5-aminopentanol is the least volatile. It is
expected that the most alkaline conditions under twophase flow conditions would be obtained with the application of 5-aminopentanol and that the application of
dimethylamine would produce the least alkaline conditions.
EPRI has conducted both field studies and laboratory
studies of neutralizing amines to establish their thermal
decomposition in fossil power plant cycles [4,5]. Both the
laboratory studies and the subsequent field studies
revealed that significant thermal decomposition of amines
occurs through the power plant cycle, in particular
through the reheater. The decomposition rate is greatest
at the highest temperatures and correspondingly lower
pressures; so although superheater and reheater outlet
temperatures are the same, the rate of amine decomposition is greater at the lower reheater pressures.
The survival of neutralizing amines in the field study fossil
and HRSG plants was between 3560 % from the condensate pump through the hot reheat depending on the
amine and temperatures, pressures, and other conditions
specific to the studied plants.
In all plant systems tested, ammonia from the decomposition of the applied neutralizing amine was the primary pH
control agent. Evaluations using EPRI's MULTEQ [17]
thermodynamic equilibrium calculation software indicated
272
More benefit was seen at one of the combined cycle

plants tested, where there was sufficient amine in the
condenser and LP drum to provide a significant increase
in the pHT of simulated two-phase conditions of early condensate and/or saturated water flashing to steam. The use
of these amines at levels sufficient to significantly increase
the pHT, however, significantly increased the cation conductivity of the feedwater and steam at the studied plant.
POTENTIAL TARGETED USES OF NEUTRALIZING

AMINES IN FOSSIL PLANTS
Based on the research to date [35], general applications
of neutralizing amines at the condensate pump discharge
will likely provide little benefit in fossil plants due to the
high degree of decomposition through the power plant
cycle, in particular the reheat section. The net result is that
very little of the neutralizing amine is available for the
intended use within the cycle, it having been replaced by
the thermal decomposition products of ammonia, acetate,
formate and carbon dioxide [35].
Two-Phase Flow-Accelerated Corrosion

Based on their distribution and dissociation properties
many neutralizing amines should result in a significant
increase in the pH at operating temperature (pHT) under
two-phase flow conditions. However the application of
neutralizing amines at the condensate pump discharge is
unlikely to achieve these improvements due to the high
degree of thermal breakdown through the superheater
and reheater of the conventional fossil plant operating
with steam temperatures at 538 C or greater. MULTEQ
simulations [17] done for field study units which applied
amines at the condensate pump discharge found that the
presence of ammonia and acetate from the thermal breakdown of the applied amine was the dominant factor in
determining the two-phase pH throughout the heater drain
system of the field plants [4]. Simulations however did
indicate that an improved two-phase pH could be
obtained if the neutralizing amine were added downstream of the reheater (e.g. directly into steam extraction
lines) as this would result in the neutralizing amine reaching the two-phase environment without first passing
through the superheater or reheater. Continual feed of the

neutralizing amine would be required to sustain the
improved pH due to the breakdown of the amine after it
passes through the superheater and reheater. There would
also be a net increase in cation conductivity from the
formation of acetate, formate and carbon dioxide. It is
impossible to say whether the net effect would result in
any corrosion rate improvements, despite the improved
calculated pHs due to the build-up of acetate and formate. If the unit applied a full flow condensate polisher
this would prevent the formation of thermal breakdown
products and it would be expected that in this case there
should be a net corrosion improvement. However this
expectation is based on simulations and no field testing
has been done to confirm if this would be seen in an
actual application.
Steamside Corrosion in Air-Cooled Condensers (ACC)

Many neutralizing amines based on their distribution and
dissociation properties could improve two-phase pH conditions within ACCs. This should reduce steamside corrosion in these components, and field work reported by
Stroman [18] has confirmed a reduction in corrosion
product generation after the application of a blend of
2-aminoethanol (ethanolamine) and ammonia, versus
operation with only the addition of ammonia. In high-pressure units with superheat and reheat temperatures greater
than or equal to 538 C this would require that the neutralizing amine be applied in the LP turbine or exhaust duct
from the LP turbine to the ACC to prevent thermal decomposition from eliminating the neutralizing amine prior to
introduction into the ACC. A unit with a full flow condensate polisher applying a blend of neutralizing amine and
ammonia would be expected to have improved corrosion
control results versus a unit applying simply ammonia. For
a unit that does not have a full flow condensate polisher
the formation of acetate and other neutralizing amine
decomposition products may negate all or some of the
benefits from the application of the amine.
Steam Turbine Phase Transition Zone

The application of neutralizing amines directly to the IP-LP
turbine crossover may result in improved early condensate
and liquid film pH conditions. This improvement though
might be negated if the unit does not have a full flow condensate polisher by the presence of thermal breakdown
products of the amine such as acetate and formate. The
application of an amine prior to the superheater/reheater
in units with steam temperatures greater than or equal to
538 C would have a net neutral or potentially a net negative effect on the pH of early condensate due to the formation of thermal breakdown products and relatively little of
the amine surviving the cycle to reach the phase transition
zone of the turbine.
PPCHEM
CONCLUSIONS
Amines can and do have a role in power plant cycle chemistry. The stronger alkalizing capability of many amines,
compared with ammonia, particularly at high temperatures,
and the stronger affinity for the aqueous phase of some
products would provide a means to reduce the risk of flowaccelerated corrosion (FAC). Single-phase FAC is most
likely to occur at 180200 C, where the solubility of magnetite is highest, in the feedwater heaters and connecting
pipework and has resulted in catastrophic failures and
occasional fatalities. Two-phase FAC occurs in the evaporation zone, when droplets of water impinge on materials.
Increasing the local (surface condition) pH reduces the rate
and occurrence of single- and two-phase FAC.
FAC in fossil and nuclear plants in the wet steam regions is
a continuing concern. Conversion of components to FACresistant materials does not represent a viable economic
option for many existing (and perhaps new) power plants.
Similarly, materials for construction of air-cooled condensers (ACC) and heat recovery steam generators
(HRSGs) will continue to be corrosion susceptible materials. Alternative amines offer substantial benefit in the distribution into the condensing steam to elevate the pH at the
operating temperature to a region of minimum corrosion.
In the phase transition zone (PTZ) of LP steam turbines,
amines will improve the pH conditions of the early condensate and may offer other benefits. Amines may reduce the
risk of acidic conditions forming in the PTZ of the turbine,
reducing the risk of corrosion. Experience in nuclear steam
turbines (in pressurized water reactor (PWR) units) particularly in the U.S. has not demonstrated any detrimental
effects from the decomposition products from the use of
amines [19], however the elevated temperatures of fossil
and HRSG superheaters and reheaters represent significantly greater potential for thermal decomposition to
acetates, formates, and carbon dioxide.
While the pressures and temperatures of the PWR test
conditions are much lower than the maximum conditions
typical of fossil plant and HRSG cycles, the nuclear PWR
research data provides a major premise for the characterization of amines in the areas of concern in fossil plant and
HRSG systems. However, case studies and operating data
from fossil plants and HRSGs currently using (or having a
past history of using) the alternative amines demonstrate
cation conductivity values that indicate substantially higher
rates of thermal decomposition resulting from exposure to
temperatures approaching 550 C.
Although amines with suitable basicity and volatility characteristics can be identified, one potential hindrance to
their use for pH control is their finite thermal stability. Many
amines are susceptible to rapid hydrolysis or oxidation at
elevated temperatures. Aside from decreasing the amine
concentration and reduction in buffering capacity, amine
273
PPCHEM
decomposition may generate a variety of reaction products. Some of the decomposition products such as ammonia or other amines are generally harmless; however, oxidation commonly yields small concentrations of carboxylic
acids or CO2, which may pose a threat to wet steam piping.
An increased understanding of the direct impact of the
weak organic acids from thermal decomposition on corrosion mechanisms of boiler tubes and turbine components
is required before complete acceptance of amines for use
in high-pressure operating systems can be endorsed.
REFERENCES
[1]
Comprehensive Cycle Chemistry Guidelines for Fossil

Plants, 2011. Electric Power Research Institute, Palo
Alto, CA, U.S.A., 1021767.
[2]
Loop Testing of Alternative Amines for All-Volatile

Treatment Control in PWRs, 1992. Electric Power
Research Institute, Palo Alto, CA, U.S.A., TR-100756.
[3]
Assessment of Amines for Fossil Plant Applications,

2010. Electric Power Research Institute, Palo Alto,
CA, U.S.A., 1017475.
[4]
Interim Guidance Amine Treatments in Fossil Power

Plants, 2010. Electric Power Research Institute, Palo
Alto, CA, U.S.A., 1019636.
[5]
Thermal Degradation of Amines in Supercritical

Water, 2010. Electric Power Research Institute, Palo
Alto, CA, U.S.A., 1021499.
[6]
Ball, M. (Consultant), 2006.
[7]
Holroyd, N., Parkins, R., Corrosion Science 1980, 20,

707.
[8]
Parker, J., British Corrosion Journal 1973, 8, 124.
[9]
Parker, J., Pearce, W., Corrosion 1974, 30(1), 18.
[10] Maeng, W., Macdonald, D., Corrosion Science 2008,

50(8), 2239.
[11] Jonas, O., Machemer, L., Proc., 8th International
Conference on Cycle Chemistry in Fossil and Combined Cycle Plants with Heat Recovery Steam
Generators, June 2022, 2006, 2007 (Calgary,
Alberta, Canada). Electric Power Research Institute,
Palo Alto, CA, U.S.A., 1014831, 9-2.
[16] Deak-Phillips, A., Morpholine Usage for pH Control

Cliffside Steam Station, 1992. Duke Energy Corporation, Charlotte, NC, U.S.A.
[17] MULTEQ Version 4.0 Desktop Application, 2006.
Electric Power Research Institute, Palo Alto, CA,
U.S.A., 1014414.
[18] Stroman, W., Chemistry Change to Address FAC-like
Corrosion in ACC Tubes, 2009. Presentation at the
meeting of the Air Cooled Condenser User Group,
Las Vegas, NV, U.S.A., November 1213, 2009.
[19] Millett, P. J., Fruzzetti, K., Proc., International Conference on the Interaction of Organics and Organic
Cycle Treatment Chemicals with Water, Steam, and
Materials 2005, 2006 (Stuttgart, Germany). Electric
Power Research Institute, Palo Alto, CA, U.S.A.,
1013630, 13.
Paper presented at the 3rd International Conference

Interaction of Organics and Organic Cycle Treatment
Chemicals with Water, Steam, and Materials, Heidelberg,
May 2123, 2012.
THE AUTHOR
James A. (Jim) Mathews (B.A., Zoology and Chemistry,
Indiana University, Postgraduate Work, Nuclear and
Corrosion Engineering, North Carolina State University,
both in the U.S.A.) is the program manager for the Boiler
and Turbine Steam and Cycle Chemistry Program at the
Electric Power Research Institute (EPRI) in Charlotte,
North Carolina, U.S.A. Before joining EPRI in 2007 he was
the corporate consulting chemist for fossil generation at
Duke Energy, where he supported fossil chemistry
programs for 36 years. Jim Mathews is a member and
past chair of the ASME Research Committee on Power
Plant and Environmental Chemistry. He has authored
numerous papers both nationally and internationally on
ion exchange, biofouling, chemical cleaning, and cycle
chemistry.
[12] Svoboda, R., Sandmann, H., Gabrielli, F., PowerPlant

Chemistry 2000, 2(2), 75.
[13] Martynova, O., Vainman, A., VGB Kraftwerkstechnik
1997, 77(8), 597.
[14] Vasile, S., Report for Internal Decay Problems of
Boiler Tubes in Units I, II, and III of Ptolemais Power
Plant and Their Chemical Control, 2007. Public Power
Corporation S.A., Athens, Greece.
[15] Carneiro, J., Dobson, T., Chiarotto, F., Report on Tests
of Alternative Amines for Feedwater Conditioning at
Lambton TGS, Unit 2, 1985. Ontario Hydro, Lambton
Generating Station, Courtright, ON, Canada.
274
CONTACT
James A. Mathews
Electric Power Research Institute
Generation Sector, Steam and Cycle Chemistry
1300 W WT Harris Blvd.
Charlotte, NC 28262
U.S.A.
E-mail: jmathews@epri.com
PPCHEM
Events
This column contains information on conferences, workshops, meetings, etc.,

important for power plant chemistry. We intend to inform our readers about
events which will take place in the near future.
Event
32nd Annual
Electric Utility Chemistry Workshop
Hawthorn Suites by Wyndham Champaigh, Chapaign, IL, U.S.A.
June 57, 2012
About the Workshop

Now in its 32nd year, this comprehensive program features state-of-the-art information on controlling
corrosion, improving operation efficiency, and meeting environmental challenges in fossil- and nuclearfueled power plants. This year's program is geared toward improved training and continuing education
of personnel responsible for electric utility cycle and environmental chemistry.
More than 3 000 chemists, consultants, and power plant administrators have attended the workshop
since its inception in 1981. The 2012 program has been developed by a committee of representatives
from midwestern electric utilities, the Illinois State Water Survey, the University of Illinois at UrbanaChampaign, and consultants serving the power industry.
Some of the most popular features of the workshop are the utility experience presentations. Seasoned
professionals from utility companies discuss their experiences on a range of topics. The entire workshop has been structured to encourage participation from attendees.
The Electric Utility Chemistry Workshop will feature an optional pre-workshop seminar on the basics of
an important aspect of power plant water treatment. This half-day training seminar on the Tuesday
morning, June 5 will provide information on makeup water treatment.
Who Should Attend

This workshop is specifically designed for personnel involved in day-to-day decisions affecting the
performance of electric utility generation in fossil-fueled and nuclear power plants. The program applies
equally to power plant chemists and engineers as well as power plant designers and consultants,
industrial and institutional plant engineers, managers and operators.
Personnel new to power plants should consider attending the Tuesday morning seminar that is
designed as a training workshop.
Source:
http://www.conferences.uiuc.edu/conferences/conferenceviewer2/view.cfm?conf=20041
275
PPCHEM
Events
22013
3
Calll for Papers
Paperrs
Call
Sponsorrship & Exhibition
Exh
hibitio
Sponsorship
Op
pportunitiess
Opportunities
MARCH
M
A RC H 26T
2 6 T H-28TH,
H - 2 8TH
H, 2013 W
WA
A SH IN
INGTO
ON
N DC U S A
276
PPCHEM
Events
Flow-accelerated
Flo
w-a
accelerat
a ed Corrosion
Corr
rosion (FAC)
(F
FA
AC)
in Fossil and Combined Cycle/HRSG

Cycle
y e/HRSG Plants 2013
2013 International Conference
Call for Papers
Pape
ers and Initial Information
Inforrmation Tuesday, March
ch 26, 2013 - Thursday, March 29, 2013
Associa
Associated
ated
Organiza
g
ations
Organizations
CEA
CEATI
ATI International/Centre
International/Ce
l/ entre for
f Energy
Advancement through
h Technological
Technological
Innovation
Innovatio
on
e Journal
Journal
Combined Cycle
Electric Power Research
Researcch Institute (EPRI)
International
International Association for
f the Properties
Properties of
Water
W
ater and Steam
m (IAPWS)
PowerPlant Chemistry
Chemistr y Journal
Journal
Structural Integrity Associates,
Asssociates, Inc.
The 2013
13 Inter
International
national Conference
ce marks the second gathering
ng of technical
experts and
nd end users to focus on allll aspects of FFAC
AC in fossil and
d combined cycle
systems. The
held
e inaugural
i
l conference
f
hel
h
l in
ld
i 2010 was attended
tt d d by
b 170 people
l from
f
21 countries and
with 40 papers. The conference will
nd featured a technical program
program
g
be linked to the
de
e 2013 FAC
FAC Conference, May
ay 21-24, 2013, organized by lectricit
industry.
France, which focuses
cuses on FFAC
AC in the nuclear p
power industr
y.
Westin
n
Arlington
n
Gateway
y
(1) 703-7
703-717-6200
17-62
200
801
North
Road
801 N
orth Glebee R
oad
Arlington,
Arlington, VA
VA 22203
22
2203
USA
USA
The 2013
International
(FAC)
013 Inter
na
ational Conference on Flow-accelerated
a
ccelerated Corrosion (F
AC) iin
n Fossil and
Combined Cycle/HRSG Plants will be held on March 26-28, 2013. Total
otal
o
al attendance is
targeted
180
geted
d at 18
80 people.
peop
ople. The conference will
w include an Exhibition Area
a and is seeking
exhibitors
sponsors
supportt variouss conference activities. An Exper
Expert
xhibitors and
d sponso
ors to suppor
xpert Panel and
Roundtable
Discussion
oundtable D
Disccussion
n is planned for the morning
morning of March 29.
Who sho
should
ould
d at
attend
tend the co
conference?
onference?
Anyone invo
involved
olved with
w FAC,
F
including researchers,
earchers, industr
industryy personnel (including
engineers,
ngineers, chemists,
ch
hemistts, op
operators
perators and managers),
agers), and technical product and ser
services
vices
organizations
ganizationss willl benefit
bene
efit from attendance.
e.
SummaryAgenda
Su
mmaryAgenda
d
Day 1: Tuesday
Tuesday,
T
uesday
y, March
h 26
07:00 Registration/Exhibition
n Open
08:00 to 17:00 Conference Sessions
17:30
17:30 to 19:30 Social and Networking
Networkking Gathering
Wednesday,
Day 2: Wednesday
W
ednesday
y, March
rch 27
17:30
0 to 20:00 Conference Reception
on and Buffet in
Exhibition Area
Day 3: Thursday,
Thursday
y,, March
March 28
17:00
Adjourned
Exhibition
17:0
00 Conference Adjour
j ned / Exh
hibition Closed
Friday,
Day 4: Friday
y,, March
h 29
Experts
08:00 to 12:00 FFAC
AC Exper
tss Panel
and Roundtable Discussion
on
277
PPCHEM
Events
Call for Con

Conference
nference Papers
The conference will co

2, to
consist
onsist of both invited and contributed
uted technical papers. Abstracts
ts must be submitted by September
ber 30, 201
2012,
guarantee consideratio
g
men. Authors will be notified of acceptance
on byy the conference chair
eptance
p
p
consideration
chairmen.
byy October 31,, 2012. Authors of accepted
papers should be prep
pared to submit the completed paper
aper and/or presentation materials
rials by February
Februar y 15th, 2013.
prepared
Person to receive
e abstracts: Barr
Barryy Dooleyy via bdooley@structint.com
y
Sub
Subjects
bjects to be covered during
ing the conference include:
include:
Q F
FAC
AC in Fossil Plants
Q Conventional Fossil Power P
Plants
Q Combined Cycle Plants with
h Heat Recover
Recoveryy Steam Generators
Gene
erators
Q F
FAC
AC in Other Industries (Refineries,
( fineries, Pulp
p and Paper,
Paper
p , Dairies
Dairries and Food
Supply Systems, Industrial St
Steam
team Plants, City Steam and Water
Water Supply
Systems, Geother
Geothermal,
mal, etc.)
Q Cycle Chemistr
Chemistryy Influences on FAC
FAC
Q Materials Aspects of F
FAC
AC
Q F
FAC
AC Research Activities
Q F
FAC
AC Damage Mechanisms
Q F
FAC
AC Modeling
Q Programs for Management of F
FAC
AC
Q Predictive Methods
Q Inspection and NDE T
Technologies
echnologies
logies
Q Repair
R
i and
d Replacement
Q Life Management
Q End User Experiences
Conference International Adv

Advisory
visory Group Memb
Members
bers
Q
Q
Q
Q
Q
Q
Q
Q
Q
Q
Q
Q
Q
Q
Q
Q
Q
Q
Q
278
David
d Addison,
dd
Thermal
Ther
h mall Chemistry,
Chemistr
h
y, New Zealand
Zealand
l d
Bob Anderson, C
Competitive Power Resources,
Resourcess, USA
Dr.. Geoff Bignol
Dr
Bignold,
ld, GJB Consulting, UK
Professor Alber
Albertt Bursik, PowerPlant Chemistr
Chemistry,
y, Ger
Germany
many
Darryl
D
Darr
yll Glanton,
Gl t
EPRI,
EPRI USA
TTom
om Gilchrist, TTri-State
r
ri-State
G&T
G&T,
T,, USA
Andy Howell, Xc
Xcel
cel Energy,
Energyy,, USA
Garyy Joy
Gar
Joy,
y,, CS Energy
En
Energy,
nergyy,, Australia
Dr.. Zhigang Li, TTPRI, China
Dr
Professor Derek Lister
Lister,, University New Brunswick,
Brunsw
wick, Canada
Des McInnes, St
Stanwell,
tanwell, Australia
Keith Nor
Northcott,
thcott, Eskom, South Africa
Professor Tamara
Tamara
a Petrova, Moscow Power Institute,
Insstitute, Russia
Michael Rziha, S
Siemens, Germany
Germany
Professor Hirosh
Hiroshi
hi Takaku,
Takaku,
akaku Shinshu University,
Universityyy, Japan
p
Stephane TTrevin,
revin, lectricit de France (EDF), France
Professor Shunsh
Shunshuke
huke Uchida, JAERI, Japan
Stan W
Walker,
Walker
alker, EP
EPRI,
PRI, USA
Daniel Zineman
Zinemanas,
as, Israel Electric, Israel
PPCHEM
Events
Conference Sponsorship & Exh

Exhibition
hibition Opportunities
ities
Conference Spon
Sponsor/Exhibitor:
nsor/Exhibitor: $2500.00
0
includes:
Sponsorship include
s:
Q Company name
e and logo displayed on conf
conference
ference signage in registration
on area and at
conference rece
reception
ption and on conference web
website
bsite page with description (50
50 words or less) and
link to company
ys home page
companys
Q One complimen
complimentary
tar y table top exhibit
Q One complimen
complimentary
tar y registration to all confer
conference
rence activities
Q Acknowledgeme
Acknowledgement
ent by Conference Chairmen
Chairmen at various points in the program
gram
Spon
nsor: $1500.00
Conference Sponsor:
Sponsorship include
includes:
s:
Q Company
p y name
e and logo
g displayed
p y on conf
conference
ference signage
g g in registration
g
on area and at
conference rece
reception
ption and on conference web
website
bsite page with description (50
50 words or less)
and link to comp
companys
panys home page
Q Acknowledgeme
Acknowledgement
ent by Conference Chairmen
Chairmen at various points in the program
gram
Conference Exhibitor:
Exhib
bitor: $1500.00
gram and exhibition space has
as been designed to offer exhibitors
hibitors maximum
The conference prog
program
opportun
nities with conference attende
ees. The conference reception
on and mor
ning/
networking opportunities
attendees.
morning/
afternoon breaks wi
diisplay area.
afternoon
willll be held in the exhibition display
age includes the following:
The exhibition packa
package
Q One 6 foot skir
skirted
te
ed table, two chairs, one wa
wastebasket
astebasket and one electrical outlet
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complimentary
l
tar y registration to allll confer
conference
f rence activities
Q Company name
e will be posted on conferenc
conference
ce website page
Q Additional exhib
exhibit
bit staff may register for redu
reduced
ced rate of $600.00, which allows for par
participation
ticipation
in the exhibit are
area
ea and all food functions
Conference Website and Regi

Registration
istration
As infor
information
mation becomes
beco
omes available it will be posted
ed on the conference website.
e.
www.facfossilhrsgconference.com
www
.facfossilhrsgco
g onference.com
and
Registration for the Conference,
C
Sponsorships an
nd Exhibition will open May 31st.
3
279
PPCHEM
Events
nformation
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hairs:
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Area Inform
D.C.,
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280
PPCHEM
Dear plant manager,
You have received a free copy of our PowerPlant

Chemistry journal for review. Why should you be
interested in a journal covering exclusively power
plant chemistry topics? Because I am sure that your
professional experience confirms the often-ignored
fact that good power plant chemistry helps the operator in improving the availability, reliability and economics of the plant.
ANALYTICAL INSTRUMENTS
AMI Inspectors Portable Inspection Equipment

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Two equations demonstrate this in a very simple and

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less failure of and damage to major plant cycle
components +
markedly fewer or no chemistry-related outages +
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fewer other chemistry-related problems
Please have your chemist or engineer in charge of

chemistry in your plant review this journal. Send me a
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281
PPCHEM
A Practical Guide to Investigating Operating Problems on In-situ Regenerated Polishing Mixed Beds
A Practical Guide to Investigating Operating Problems on

In-situ Regenerated Polishing Mixed Beds
Brian Windsor and David Hayhurst
ABSTRACT
This paper looks back at the historical problems that are still being frequently encountered on polishing mixed beds,
these being typically apparent as very long rinse times to quality after regeneration, or consistently poor treated water
quality (high conductivity). Over 95 % of mixed bed problems are caused by one or more problems in the following
four areas of regeneration: poor resin separation, inadequate slow displacement rinsing, poor drain control prior to
remixing, and air blowers. This article is designed to help plant chemists and operators in troubleshooting mixed bed
problems by identifying the issues involved, as well as to give all readers a better understanding of polishing mixed
bed operation.
INTRODUCTION
Conductivity at 25 C
Sodium
[S cm1]
0.060.1
< 0.01
< 0.02
[mg L ]
Most ion exchange issues are rarely due to problems with

the resins themselves, but are primarily due to aspects of
the operation of the plant. The units which provide the
biggest challenge to operators of make-up demineralisation plant are polishing mixed beds. These problems were,
in the main, identified twenty to thirty years ago in the
power industry.
Table 1:
Recent years have seen a recurrence of these issues, with

customers requiring on site support for troubleshooting
mixed bed problems more frequently than for any other
type of unit. In the vast majority of cases the problem of
poor quality is due to one or more of the four problems
outlined below, and thus this article is designed to serve
as a troubleshooting refresher to plant chemists and operators.
To achieve this quality polishing mixed beds should never

be run to exhaustion and the service cycle should be
terminated on time or throughput well before any increase
in conductivity or reactive silica is seen. This way the
resins are maintained in optimum condition and almost
fully regenerated, and this premature regeneration does
not add much to the operating costs of running the plant,
as the bulk of the costs is in the acid and caustic used in
the preceding cation and anion units.
Reactive silica
[mg L ]
Typical make-up plant polishing mixed bed quality.
Mixed Bed Performance

When treating partially demineralised water which has
passed through a cation and anion stage or reverse osmosis plant, the polishing of this water should result in a final
treated water quality that complies with that defined in
Table 1 at all times.
Conductivity is very temperature sensitive so any measurement needs to be with a temperature compensated
instrument and any silica guarantee can only relate to
reactive silica. Non-reactive (colloidal silica) is not fully
removed by conventional mixed bed ion exchange resins.
REGENERANT INJECTION OPTIONS

While the valve arrangements are similar on all mixed bed
designs, some companies do carryout the regeneration
slightly differently. The biggest difference is often in the
regenerant injection stages.
The modern way of introducing the regenerant, after separating the resin into its cation and anion components, is
to have the acid and caustic injection occurring simultaneously, with the caustic introduced from the top and the
acid from the bottom and with both regenerants leaving
282
via the centre collection system located at the interface of

the two resin components. The slow (displacement) rinses
follow the same route.
Other systems are designed using the same regenerant
injection points but do not carry out the injection simultaneously. These designs usually introduce the caustic first
and have an upward water buffer flow through the cation
component to stop caustic migration. Likewise the caustic
rinse provides a downflow buffer during upward acid
injection. Another variation is where the caustic and acid
injection are carried out totally separately, and here the
acid is introduced downflow through the centre collection
system.
PPCHEM
required to decompact the bed, loosen the resin for better

regenerant contact and most importantly to separate the
intimately mixed resin into its two separate components of
cation and anion resin. If the mixed bed uses a separating
inert of intermediate density, then the backwash will separate the bed into the three components.
On some occasions return condensate is introduced for
polishing and is mixed with the water from the anion column. The condensate can contain suspended solids and
in this case the backwash is also required to remove the
solids from the bed. Under these circumstances the backwash step is normally longer to ensure the bed is clear of
solids.
All the above commonly encountered designs have been

successfully employed in achieving the water quality
defined in Table 1. Regardless of the system used, this
article covers the main operating problems encountered
on polishing mixed beds employing in-situ regeneration.
After separation the beds are allowed to settle and reform

into the separate components. The bed settle step can
last 5 to 10 min depending on the volume and type of
resins used. Gel resins settle more quickly than macroporous resins.
Figure 1 provides a diagrammatic representation of these

alternative designs used in introducing regenerant.
The next stage is regenerant injection utilizing any of the

routes described earlier in the paper. Acid regeneration
levels are typically between 50 and 70 g L1, while caustic
regeneration levels are typically higher between 60 and
80 g L1. On some occasions systems are encountered
where the caustic is warmed slightly. This tends to be
observed on older plants and was introduced to help in
the removal of silica from the anion component. Today it is
rarely used unless the silica loading is very high. The typical regenerant flow rate is 2 to 4 bed volumes (BV) per
hour and the regenerant concentrations are typically 4 %
for caustic injection and 5 % for acid injection for either
sulphuric or hydrochloric acids.
(a)
(b)
(c)
Figure 1:
Alternative regenerant introduction methods.
(a) simultaneous acid/caustic regeneration
(b) caustic injection with water buffer
(c) acid injection via centre system
MIXED BED REGENERATION CYCLES

Once the unit is taken off line and the unit is isolated (inlet
and outlet valve closed) the first step is a backwash.
Mixed beds should ideally have more than 100 % freeboard (space above the bed) and the backwash, introduced into the bottom of the unit, leaves through a backwash strainer at the top (which also often acts as the inlet
distributor for the water in normal operation). The backwash can have up to three functions.
Where the water is all derived from a preceding anion column, no solids should be present. Here the backwash is
The slow (displacement) rinse is carried out at a similar

flow rate as the regenerant injection and is designed to
remove the vast bulk of regenerant efficiently. By using a
similar flow rate the rinse water follows the same path as
the regenerant from the distributor and hence good plug
flow would be expected to be achieved.
Having rinsed the bulk of the chemical from the two components the resins must be remixed. This is done by first
draining down the water level to just above the bed and
then introducing an air mix stage to mix the resins. The air
is normally supplied by separate low pressure air blowers
or occasionally via site air. The air needs to be clean and
oil free; an air velocity of around 110 m3 m2 h1 is
required within the unit and usually a pressure around
5 bar.
Once remixed the unit is refilled. Usually the initial fill is via
the caustic distributor first so as not to disturb the bed and
then once the bed is well covered with water a higher flow
rate is used from the top of the unit to complete the filling.
283
PPCHEM
The final stage is a rinse to drain to achieve final quality.

This rinse is usually quite quick as any trace acid from the
cation resin is removed by the anion component while any
caustic from the anion component is collected by the
cation resin. Some plants have a rinse recycle stage to
reduce rinse water requirements further.
A typical mixed bed arrangement is illustrated in Figure 2.
Backwash water outlet

Inlet
Air vent
Acid
regeneration
gear
Caustic
regeneration
gear
Centre
drain
Final rinse
to drain
Air inlet
Backwash water inlet
Floor
drain
Treated water outlet
after the chemical draw step, stopping the regeneration

and refilling the chemical measures. The chemical injection step can then be repeated and the unit allowed to
proceed through the remainder of the regeneration cycle.
The important action during this double regeneration is for
an experienced operator who understands how the plant
works to check some of the basics. First, before starting
the double regeneration, check that the resin level is correct (easy if there is a top sight glass) to make sure the unit
has not lost any resin. Lost resin can affect not only the
units capacity between regenerations but also the interface position after backwashing and the resin mixing
stage, all of which will result in poor quality. The operator
should also check that the chemical measures are filling
correctly and the full amount of regenerant is being
applied during the chemical draw stage. The valve
sequences must be confirmed as correct and opening and
closing at the right time. In addition the air blower must be
working correctly, the air relief valve should not have lifted
and thus the full air flow should pass to the vessel for resin
mixing.
Hopefully, when the regeneration cycle has been repeated
and if no issues have been identified, the mixed bed will
return on line with no quality issues. If however the problems persist or if the problem has been a slow deterioration in performance, then a more detailed investigation is
required.
The major problems reported on mixed beds can mainly
be split into the following categories:
very long rinse times to quality
poor water quality (high conductivity) at all times.
Rinse recycle
Figure 2:
During regeneration there are four areas which can lead to

poor quality and over 95 % of mixed bed problems are
caused by one or a combination of the issues listed below.
Typical mixed bed arrangement.
Poor Resin Separation
POOR MIXED BED PERFORMANCE

It is very unusual for any ion exchange to be working perfectly and then suddenly begin to perform very badly.
When this type of catastrophic failure occurs, it is usually a
relatively simple problem, can normally be found very easily and is usually due to a problem on the previous regeneration. The recommended first action is to put the mixed
bed through a double regeneration to ensure the resin is
fully regenerated and the resins are both in the best possible condition. Hopefully this will address the problem.
A double regeneration can be performed by carrying out
the full regeneration procedure twice (back to back), or to
quicken the process, putting the unit into regeneration and
284
Today the resin suppliers produce graded products of different density whereby mixed bed resin separation into
the two components on backwashing is achieved very
easily. It is critical that the interface between the lighter
anion resin (on the top) and the heavier cation resin (on the
bottom) is located in the correct position. This is because
it is important that the sodium hydroxide (caustic soda)
used to regenerate the anion component does not contact
cation resin as it will convert it to the sodium form; likewise
it is important that the acid usually either sulphuric acid
or hydrochloric acid does not contact anion resin as it
will be converted to the sulphate or chloride form depending on the acid used. Of the two, anion contamination with
acid causes more long-term problems than a little caustic
in contact with cation resin. Therefore, when commissioning a new resin charge it is usually impossible to get the
interface exactly on the midpoint of the centre laterals and
so the recommendation is that the lateral slightly favours
the cation resin (but is not buried in the cation!). This will
still give very good performance as slight sodium contamination of the cation is not highly detrimental to performance.
Obviously from this information operators should realise
that special care should be taken when loading/commissioning new mixed bed charges. Purolite have produced a
written guide to assist companies loading mixed bed
resins to ensure good performance.
All mixed beds should have a minimum of one sight glass
located in line with the centre laterals so that operators
can check the interface position. It is recommended that
when there is no resin in the unit, the position of the lateral
should be carefully drawn/marked on the sight glass to
show the position when the bed is full of resin. This
enables operators to check the position routinely and this
is very important when there is a mixed bed quality problem.
If the interface is too low and the bed has backwashed
correctly, then the most likely cause is loss of some of the
cation resin. While this must be investigated to find the
cause of the loss, short term the problem can be corrected by adding some more bags of cation resin to the
bed and giving the unit a double regeneration. If the resin
loss is small and results from minor damage to a centre
lateral or bottom lateral, then it is possible to collect the
lost resin by putting a bag filter over the drain outlet to
recover the resin and to use the collected resin to top up
the bed regularly until a full repair can be accommodated.
Obviously major losses cannot be handled in this manner
and a full repair must be undertaken.
Where lost anion resin is identified, i.e. the resin bed is low
but the cation interface is in the correct position, then this
usually means either the backwash rate is too high, forcing
anion resin out of the column (or damaged top strainer), or
there is damage at the centre lateral causing anion resin
loss during caustic injection and slow rinse.
If the interface is too high, this can be due to resin coming
into the bed from the preceding unit, but is more likely
caused by trapped anion within the cation component.
This is where the backwash rate is too low (it usually
occurs in the summer with higher water temperatures) and
requires an increased rate to expand the cation fully so
that entrapped anion resin can escape.
If the backwash flow is increased too much and the flow
rate falls, this is because the rate is too high and the lighter
anion resin has been pushed around the top strainer/col-
PPCHEM
lector causing blockage; therefore the rate needs reducing

a little.
If however the backwash works well and the resin interface is in its correct position, then we need to look at other
likely causes.
Inadequate Slow Displacement Rinsing

As we have seen, there are different routes used on mixed
beds for introducing acid and caustic, the most popular
being simultaneous injection with the regenerant and slow
rinses leaving from the buried centre drain.
However, regardless of the system used there is never a
conductivity meter on the centre drain and the conductivity at the end of the slow rinse is not monitored. It should
be relatively low showing that all the regenerant chemicals
have been washed from the bed. Normally the system just
relies on the fact that sufficient slow rinse has been introduced when originally commissioned. Unfortunately, collection/distribution systems do get blocked and flow rates
and pressures do change. So after having gone to all the
trouble of making sure the beds are perfectly separated to
stop contamination, it would be counter-productive to
leave lots of regenerant in either component before remixing!
This has been found to be a common cause of quality
problems on many mixed beds, and on some occasions, if
the laterals/nozzles are not too badly blocked, the issue
has been addressed temporarily just by extending the
slow rinse stage. A full inspection of distributors and collectors to make sure they are clear and working correctly
can then be made when time allows.
To check this problem, take samples of the water leaving
the unit at the end of slow rinses and check the conductivity it should be low, preferably less than 50 S cm1. On
some units conductivities exiting the centre drain at the
end of the slow rinse of over 1 000 S cm1 have been
observed, resulting in major cross contamination after the
remixing stage!
Poor Drain Control Prior to Remixing

Over the last 30 years, Purolite have, like all other major
resin producers, spent considerable time producing better
mixed bed grades which separate more easily and in
some cases use lower backwash flow rates. Conversely,
they are a little more difficult to remix.
Therefore ensuring that the remixing stage works perfectly
is highly critical if operators are to achieve a correctly
mixed resin charge to return to service.
285
PPCHEM
Rather surprisingly perhaps, the height that the water is

above the bed when starting the air mix is very critical. It
should be only a few centimeters above the bed (3 to 4 in).
If it is below the top of the bed, the air will not remix the
bed, and this is easily evident by looking through the centre sight glass. However, the most common problem is
that the water height is too high for modern resins.
Some years ago, engineering companies would include a
separate drain down valve from the shell of the unit with a
strainer that ran to drain. This exactly controlled the height
of the water on drain down and when the line was no
longer passing water it would be clear that the water was
at the correct height for a full resin bed and the air blower
could be started to air mix the bed.
Today, this valve is rarely seen, as almost every company
has tried to reduce costs by omitting this valve and
instead relying on setting the system up on commissioning with drain down via the centre drain and bottom drain
outlets and the control system keeping these open for a
certain fixed time. This will never work consistently over
the life of the mixed bed!
During the life of a mixed bed unit, laterals become
blocked, damaged, or replaced, valves are serviced or
replaced, resin types are changed and different grades
used. Water density also changes with temperature so
drain down can be a little slower in the winter. All of these
factors will mean that it is likely that too much water can
be left in the bed.
When there is a little too much water in the bed the air mix
always appears to go well with lots of movement and so
operators are usually pleased. In fact some operators start
the air blowers early as they know the mixing looks better
when there is more water in the bed. Unfortunately, though
the mix is better, when the air mix is stopped the resin has
expanded into the full volume, and as resins are designed
to separate better, the cation resin is often much heavier,
particularly if you have a combination of a gel cation with a
macroporous anion resin. The cation will fall very quickly
and form a separate cation layer below the mixed portion
of the bed. With no anion resin present to mop up trace
acid from the beads during the final rinse stage, the rinse
will become poor, very long and have an acid pH.
Measuring pH on the final rinse is therefore a good way of
identifying this issue.
Unfortunately, depending on the design, getting the water
height position right on your bed can be very difficult if you
have no top sight glass above the resin bed!
Some companies resolve this problem by extending the
air blower mixing stage after the drain down and then they
introduce another drain down before the end of the air
mix. This locks the fully mixed resins in place when the
286
water level falls below the bed level and stops the secondary separation of the cation component.
Air Blowers
Earlier it was noted that a velocity in the bed of around
110 m3 m2 h1 is required for good mixing and the air
blowers have to have sufficient head to blow this velocity
against the head of water and resin. Air blower failures are
not uncommon, and problems like lifting relief valves due
to high back pressure will cause loss of flow.
Always check air blowers and maintain them in good condition, and check for pipework damage from the blowers
to the unit in case some air is being lost. All these have
been identified on sites over the last 20 years as being the
cause of mixed bed problems.
A modern trend is to use site air from compressors and
not to use dedicated blowers. However, this has also been
found to be a problem if the mixed bed demand for air
mixing (which is an infrequent demand) coincides with
other major demands on site, as it can lead to a poor mix
poor performance and is almost impossible to identify as
the repeat regeneration does not coincide and the mixing
works well.
CONCLUSION
Hopefully this paper has given an insight to plant operators/managers on troubleshooting mixed bed problems by
identifying the issues the authors of this paper come
across as well as given all readers a better understanding
of polishing mixed bed operation.
While the paper was specific to in-situ make-up mixed
beds, many of the points raised would also apply to external regenerated units. External regeneration however has
one other major issue which needs care. That is, during
transfer of the mixed resin from the regeneration vessels
the resin can easily separate in the service unit if the transfer velocity is wrong for the given pipe size and more
importantly if the transfer water is not drained away immediately from the service unit as the resin is transferred
back.
Paper presented at the Annual BIAPWS Symposium on

Power Plant Chemistry, Chilwell, Nottingham, UK, March
2829, 2012.
THE AUTHORS
CONTACT
Brian Windsor (B.S., Chemistry, University of Manchester,

UK) is a technical sales manager for Purolite International
based in the UK. He has been involved in the ion
exchange industry for over 30 years since leaving university, initially working for one of the leading UK plant suppliers, Kennicott Water Treatment, and then for the last 23
years for Purolite International. Brian Windsor also acts as
the Purolite representative on the Ion Exchange Committee of the European Chemical Industry Council (CEFIC)
and on the organising committee for the SCI Cambridge
IEX 2012 Conference.
Brian Windsor
Purolite International Ltd
Llantrisant Business Park
Llantrisant
Wales
UK
David Hayhurst (Ph.D., Macromolecular Synthetic

Organic Chemistry, University of Manchester, UK) is a
technical sales manager for Purolite International based in
the UK. He became involved in the ion exchange industry
in 2008, following some years spent in various technical
roles in the pharmaceutical and food industries commercialising new products. David Hayhurst also acts as the
Purolite representative to the British and Irish Association
for the Properties of Water and Steam (BIAPWS).
PPCHEM
E-mail: brian.windsor@purolite.com
David Hayhurst
Purolite International Ltd
Llantrisant Business Park
Llantrisant
Wales
UK
E-mail: david.hayhurst@purolite.com
Sampling Systems
with high-pressure
components ...
HIGH-PRESSURE SAMPLE COOLERS
for liquid samples and steam
Design according to VGB/DGRL
Operating data:
temperatures up to 630 C;
pressure up to 400 bar;
sample flow up to 250 kg/h
... even for supercritical

steam generation
HIGH-PRESSURE VALVES
Shut-off valves Blow-out valves
Pressure-reducing valves
Fine-regulating valves
Shut-off valve units
Operating data: NW 2 - 6 mm;
pressure up to 400 bar;
temperatures up to 630 C
Sampling & Analysing Systems

3(
(1(852
32:(5* H'
VV
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, booth E
hall 11.1
287
PPCHEM
The Application of High AVT(O) in Gas Turbine Combined

Cycle Plants
Takashi Suzuki, Tetsuo Yamamoto, Masanobu Maekawa, Jun Hishida, Satoshi Kuwano, and Kazumitsu Takanishi
ABSTRACT
There is growing demand for reduced use of hydrazine at power plants due to the adverse health effects of this agent.
Moreover, many combined cycle plants are affected by flow-accelerated corrosion (FAC), especially in feedwater
systems, low-pressure boiler evaporators and other subassemblies.
Under such circumstances, modified oxidizing all-volatile treatment AVT(O) high AVT(O) was applied in the feedwater treatment system of combined cycle plants. The objective was to discontinue hydrazine injection into the feedwater, and to suppress FAC more effectively compared to AVT(O) by increasing the pH of the feedwater. Throughout
four years of operation, the water condition was measured under all plant conditions such as normal operation,
startup/shutdown operation, and unit outage for maintenance. In addition, the corrosion rate was followed closely by
measuring the piping thickness at FAC-affected points. These test data clearly showed that this water treatment could
keep ideal water conditions and is effective for suppressing FAC.
INTRODUCTION
Restrictions on the use of hydrazine in feedwater treatment at power plants and other facilities have been tightened by the Pollutant Release and Transfer Register
(PRTR) [1] and other regulations in Japan. Regulations
against hydrazine usage are also being strengthened in
other countries [2].
In 2008, modified oxidizing all-volatile treatment (AVT(O))

high AVT(O) was applied at one of our combined cycle
power plants as a trial operation, in order to eliminate the
adverse health effects of hydrazine and to suppress FAC
more effectively than with AVT(O) in the feedwater system
by increasing the feedwater pH. The water conditions and
piping conditions were closely checked and evaluated
Meanwhile, many combined cycle power plants and other

facilities operating in the world are reportedly confronting
the problem of carbon steel tube thinning caused by flowaccelerated corrosion (FAC). Such thinning is particularly
observed in their feedwater systems and low-pressure
boiler evaporators in the portions in contact with water of
pH as low as about 9.0 and temperature of approximately
160 C.
In our plants, FAC has been observed only on feedwater
tubes (Figure 1) and no cases of FAC have been found on
boiler evaporators, while many FAC failures on evaporators have been reported worldwide. Most of the
Japanese-made combined cycle power plants that commenced operation in and after 1984 for the Japanese
electric industry use a combined phosphate treatment
(CPT) system to treat low-pressure boiler water, as shown
in Table 1 [3]. Since CPT increases boiler water pH to as
high as 10, there have been no reports in Japan regarding
FAC of low-pressure boiler evaporator tubes.
Figure 1:
FAC on carbon steel in feedwater.
288
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10 MPa
1015 MPa
1520 MPa
demineralized water
demineralized water
demineralized water
AVT
AVT
AVT
Operating pressure
Makeup
Feedwater Treatment
Cation conductivity
Dissolved oxygen
> 8.5
8.59.7
pH
[mS m ]
1
<7
[g L ]
> 8.5
8.59.7
> 8.5
8.59.7
0.05
0.05
<7
<7
20*2
*1
30
Iron
[g L ]
30
Copper
[g L1]
20
10
10
10
10
Hydrazine
[g L ]
Boiler Water Treatment

pH
Conductivity
Cation conductivity
Chloride
*1
[mS m1]
PT
AVT
PT
AVT
PT
AVT
9.810.7
8.59.7
9.010.0
8.59.7
8.59.8
8.59.7
40
< 15
<6
<2
<2
10
<2
<1
<2
<1
*3
0.13.0
0.3
< 0.2
[mS m ]
[mg L ]
Phosphate
[mg L ]
*3
Silica
[mg L1]
Table 1:
General standards for heat recovery steam generators in Japan [3].
PT
*1
*2
*3
phosphate treatment
20 g L1 or less is recommended
10 g L1 or less is recommended
consistent with pH
throughout the actual plant test comparing reducing allvolatile treatment (AVT(R)), AVT(O), and high AVT(O).
OUTLINE OF HIGH AVT(O)

Definition of High AVT(O)
In Japan, the feedwater and boiler water of combined
cycle power plants are treated on the basis of Japanese
Industrial Standards (JIS) [3]. Of the two all-volatile feedwater treatment types reducing all-volatile treatment,
AVT(R), and oxidizing all-volatile treatment, AVT(O), most
plants use the former, applying ammonia for pH adjustment and hydrazine as an oxygen scavenger (reducing
agent).
In contrast to the above two treatment methods, high
AVT(O) is a modified AVT(O) that removes oxygen from the
feedwater through mechanical deaeration in a condenser
or other suitable device, without using hydrazine, and that
increases the amount of ammonia injection to increase
feedwater pH to 9.8 or more.
Objective of High pH Treatment of Feedwater

Traditionally, our combined cycle power plants have been
equipped with an AVT(R) system to control feedwater pH
within the JIS standard range of 9.39.5. Meanwhile,
Japanese-made condensers are designed to restrict the
entry of air, so as to provide a reducing condition, by controlling the dissolved oxygen concentration in the condensed water within a range of 04 g L1. This allows
both AVT(R) and AVT(O) to be conducted in a reducing
environment; therefore, the water tubes are protected
from corrosion by a protective layer composed mainly of
magnetite.
Since FAC decreases as feedwater pH increases, as
shown in Figure 2 [4], combined cycle plant operation with
high-pH feedwater was expected to minimize the tube
thinning rate.
289
PPCHEM
TEST METHODOLOGY OF HIGH AVT(O)

1 000
After studying the plant to be used for the actual test and
the water treatment method use as described below, the
test method was finalized as follows [5].
Specific Material Wear Rate [g cm2 h1 ]
500
T = 180 C
v = 39 m s1
1
DO <
5 g L
100
System Configuration of the Test Plant
50
The No. 5 combined cycle power plant (670 MW) in Himeji

No. 1 Power Station was used for the actual plant test of
high AVT(O). This plant is a multi-shaft type combined
cycle power plant consisting of one steam turbine and
three gas turbines. The main piping system and major
specifications of the test plant are shown in Figure 3 and
Table 2, respectively. The heat recovery steam generator
consists of three types of boilers: high-, intermediate- and
low-pressure boilers. Except for condensers made of titanium, the plant's main equipment is made of iron-based
materials.
T = 75 C
v = 1.6 m s1
DO = 20 g L1
10
5
1/2 Mo
2 1/4 Cr-1 Mo
0.5
0.1
Carbon steel
10
11
Water Treatment Method during Normal Operation
pH
The water quality control criteria for the actual plant test of
high AVT(O) were set with reference to JIS B 8223 "Water
conditioning for boiler feedwater and boiler water," as
shown in Table 3.
Figure 2:
Dependence of FAC rate on pH [4].
T
v
DO
temperature
flow velocity
dissolved oxygen
Heat recovery steam generator (HRSG)
Highpressure
boiler
Intermediatepressure
boiler
Lowpressure
boiler
Highpressure
turbine
turbine
Low-pressure
turbine
feedwater pump
A
Low-pressure
economizer
Highpressure
primary
economizer
To A
Low-pressure
evaporator
Intermediate-pressure
evaporator
Low-pressure
Reheater
Intermediate-pressure
superheater
Gas turbine
exhaust
High-pressure
secondary economizer
High-pressure
superheater
High-pressure
Condenser
economizer
Condensate pump
Hydrazine P
Ammonia P
Low-pressure
economizer
circulating pump
High-pressure
feedwater pump
Figure 3:
System configuration of No. 5 combined cycle power plant in Himeji No. 1 Power Station.
Piping shown in green is approx. 160 C.
290
PPCHEM
Item
Specifications
Manufacturer
Mitsubishi Heavy Industries, Ltd.
Date of commercial operation
April 1995
Generator output
670 MW: steam turbine 253 MW and 3 gas turbines 139 MW each
Type of HRSG
Triple-pressure heat recovery steam generator, drum-type (natural circulation) boilers
Fuel
Liquefied natural gas
Table 2:
Major specifications of No. 5 combined cycle power plant in Himeji No. 1 Power Station.
Treatment
pH
Feedwater
[mS m1]
dissolved oxygen
[g L1]
hydrazine
Boiler water
chloride
phosphate
silica
9.39.9 1
< 0.05
< 0.05
<7
<7
< 10 (recommended)
< 10
> 10
[g L ]
[g L ]
Boiler
conductivity
> 8.5
Treatment
pH
High AVT(O)
cation conductivity
iron
AVT (JIS B 8223)
PT
PT
PT
AVT(O)
LP and IP
HP
LP and IP
HP
9.810.7
8.59.8
10.010.5
9.09.8 2
[mS m1]
< 40
<6
< 15
<2
< 10
<2
< 0.1
< 0.1
0.13.0
<2
< 0.2
<2
< 0.2
[mg L ]
[mg L ]
[mg L ]
Table 3:
Water quality criteria for high AVT(O).
PT
phosphate treatment
target 9.8
target 9.6
consistent with pH
Water Treatment Method during Plant Startup/

Shutdown
To determine the criteria during plant startup and shutdown, a preliminary laboratory corrosion test was conducted using water tubes sampled from an actual plant.
Since this laboratory corrosion test did not raise any corrosion problem over a month, as compared to test specimens treated with hydrazine, no extra treatment was
applied for unit shutdown periods of less than one month.
RESULTS OF THE ACTUAL PLANT TEST

The actual plant test was started in 2007 by shifting from
AVT(R) to AVT(O) treatment. After confirming that this shift
did not reveal any problems with water quality, high
AVT(O) was applied as an actual plant test in 2008.
Water quality was measured in three plant operation
modes:
(1) normal operation
(2) startup and shutdown operation with the condenser
291
PPCHEM
under vacuum condition, during which the dissolved

oxygen concentration increased slowly during startup
and shutdown, and
Since AVT(R) and AVT(O) did not create any difference in

water quality, the data obtained during AVT(O) operation
are shown under "Conventional treatment" in Table 4.
(3) startup operation after long-term shutdown for periodic inspection, during which water in the plant was
saturated with oxygen.
Water Quality during Plant Startup/Shutdown

The iron concentration in recirculated condensed water
during both daily start and stop (DSS) and weekly start
and stop (WSS) of the test plant remained unchanged
independently of hydrazine injection. The iron concentration during test plant startup also remained almost
unchanged (Figure 6). An example of the dissolved oxygen
concentration change is shown in Figure 7. As this figure
shows, dissolved oxygen concentration also remained
unchanged independently of hydrazine injection, which
suggested that it would be unnecessary to inject
hydrazine when the HRSG is started/stopped with the
condenser held in vacuum condition.
Water Quality during Normal Operation

The feedwater quality and the change in iron concentration before and after high AVT(O) introduction are shown in
Table 4. As compared with AVT(O), high AVT(O) reduced
the average and minimum iron concentrations in the feedwater (temperature approx. 160 C) at the low-pressure
economizer outlet by about 35 % and about 50 %,
respectively. The cation conductivity, dissolved oxygen
concentration and other quality indicators did not
increase, verifying that the feedwater quality was equivalent to that in AVT(R) operation.
Oxidation-Reduction Potential [mV]
In connection with high AVT(O) of feedwater, the highpressure boiler water treatment was changed from phosphate treatment to AVT(O). As shown in Table 4, the boiler
water iron concentration remained unchanged; therefore
no water quality problem will arise even when the boiler
water treatment system is changed to high AVT(O).
The oxidation-reduction potentials and iron oxide crystal
forms during hydrazine injection and non-injection conditions were additionally investigated and compared
(Figures 4 and 5). The results confirmed that both the oxidation-reduction potential and the iron oxide crystal form
remained unchanged, which led us to conclude that
hydrazine injection is unnecessary.
Parameter
pH
Criteria
Cation conductivity
[mS m ]
Dissolved oxygen
[g L1]
Iron (feedwater)
Iron (boiler water)
12
0
Oxidation-reduction potential
100
10
Hydrazine concentration
8
200
Commencement of
hydrazine injection
300
4
400
500
0
0.5
1.0
Time [h]
1.5
0
2.0
Figure 4:
Oxidation-reduction potential before and after hydrazine
injection.
Conventional treatment
AVT(R) or AVT(O)
High AVT(O)
min.
max.
mean
min.
max.
mean
9.39.9
9.4
9.5
9.5
9.8
9.9
9.8
0.05
0.016
0.024
0.020
0.015
0.03
0.022
1.7
2.0
1.9
1.9
3.5
2.4
10
10
6.0
3.8
0.4
3.6
1.5
0.2
3.7
1.6
[g L ]
[g L ]
Hydrazine Concentration [g L1 ]
No resulting water quality problem was discovered in the

above three operation modes. In contrast, the iron concentration in the feedwater dropped during normal operation, suggesting that tube corrosion had been suppressed.
Table 4:
Results of feedwater condition during normal operation before and after the actual plant test.
292
PPCHEM
Figure 5:
Suspended iron oxide particles in feedwater before and after hydrazine injection.
500
AVT(O) (with hydrazine only at startup)
400
AVT(O) (without hydrazine)

AVT(R) (with hydrazine)
300
200
100
0
0
100
200
300
400
500
600
Dissolved Oxygen Concentration [g L1 ]
Iron Concentration [g L1 ]
200
Dissolved oxygen (without hydrazine injection)

Dissolved oxygen (with hydrazine injection)
150
100
During shutdown
50
Time after Startup of LP Economizer Circulation Pump [min]
0
5
0
Parallel off
5 Parallel
Time [h]
10 Parallel
Figure 6:
Figure 7:
Iron concentration in the feedwater during startup.
Dissolved oxygen concentration during startup with and without

hydrazine injection.
Water Quality during Periodic Inspection/Trial

Operation
turbines) and output (670 MW), and commenced operation with an AVT(O) system in December 2008.
Since the No. 5 combined cycle power plant in Himeji

No. 1 Power Station that was used for the actual plant test
had been inspected periodically at a frequency of once
every two years, the water quality data sampled during the
periodic inspections/trial operations was insufficient for
evaluation. To enhance the reliability of the water quality
evaluation, the data obtained from the No. 6 power plant
(made by Hitachi, Ltd.) in Himeji No. 1 Power Station were
also evaluated. The No. 6 power plant is the same as the
No. 5 plant in type (one steam turbine and three gas
Depending on the plant periodic inspection schedule, the

boilers must be kept full of water for a maximum of nearly
20 days after completion of the boiler water pressure test
until commencement of trial operation. Taking this fact
into account, water quality was measured in terms of the
iron concentration in water stored fully in each boiler, feedwater during trial operation startup and boiler water. The
measurement data were used to clarify the difference in
iron concentration change between water treatments with
and without hydrazine injection.
293
PPCHEM
The iron concentrations in boiler water stored fully in the

boilers are shown in Figure 8. This figure does not show
any difference in iron concentration between hydrazine
injection and high AVT(O), verifying that the new treatment
system will not raise any water quality problems.
500
Iron Concentration [g L1 ]
High AVT(O) LP drum
Iron concentrations in high AVT(O) and AVT(R) feedwaters

during periodic inspection/trial operation are shown in
Figures 9a and b, respectively. As these figures show, both
high AVT(O) and AVT(R) could meet the applicable water
quality criteria for heat run, although the two treatment
methods yielded a slight difference in iron concentration
due to the difference in periodic inspection work and trial
operation procedures.
400
High AVT(O) IP drum

High AVT(O) HP drum
AVT(R) LP drum
300
AVT(R) IP drum
AVT(R) HP drum
200
100
0
0
10
15
20
Number of Water Storage Days
Figure 8:
Water quality for water stored in boiler during periodic inspection.
Iron Concentration at CP Out [g L1 ]
1 000
1st GT start
ST start
2nd GT start
3rd GT start
Heat run
800
600
400
200
Water quality
stabilized
0
0
15
Time since Startup of Water Circulation in HRSG [day]
Figure 9a:
High AVT(O) water quality during unit startup after periodic inspection work.
CP
condensate polisher
GT
gas turbine
ST
steam turbine
Iron Concentration at CP Out [g L1 ]
1 000
1st GT start ST start
2nd GT start
3rd GT start
Heat run
800
600
400
Water quality
stabilized
200
0
0
Time since Startup of Water Circulation in HRSG [day]
18
Figure 9b:
AVT(R) water quality during unit startup after periodic inspection work.
CP
294
condensate polisher
GT
gas turbine
ST
steam turbine
PPCHEM
Figure 10:
Equipment inspection after the
application of AVT(O).
Inspection Results after Actual Plant Test

Amount of Scale Deposition [mg cm2 ]
20
After 3 years of operation on high AVT(O), the inside of the

drum systems and other assemblies were inspected. In
particular, the No. 5 combined cycle power plant in Himeji
No. 1 Power Station features a low-pressure economizer
equipped with a water circulation system, as shown in
Figure 3. Since the low-pressure economizer's outlet is
heated to approximately 160 C and is therefore extremely
sensitive to FAC, tubes installed in the final panel portion
of the low-pressure economizer were removed for detailed
inspection.
AVT(R) AVT(O)
15
10
In the turbine system, the intermediate-pressure turbine

exhaust goes into the low-pressure turbine, where the
steam temperature and pressure drop. As a result, scale
content that has been removed from the drum and mixed
in the steam will reduce water-solubility, and may accumulate as scale on the low-pressure turbine blades and
corrode them. To check whether or not the turbine blades
had been corroded, the condition of the low-pressure
turbine was inspected.
The conditions of the low-, intermediate- and high-pressure boiler drums were inspected. Formation of reddishbrown to black scale, composed of a mixture of hematite,
magnetite and other substances, was observed on the
inner walls of the intermediate- and low-pressure boiler
drums; black magnetite scale grew on the inner surface of
the high-pressure drum. However, no corrosion or other
defects were discovered on any drum inner surface; the
degree of scale formation and amount of deposited
sludge were about the same as in a power plant operated
on the conventional AVT(R).
20 000
40 000
60 000
80 000
100 000
Operating Time [h]
Figure 11:
Increase in amount of scale deposition on low-pressure
economizer tube surface.
The conditions of the low-pressure economizer tubes

before and after the actual plant test of AVT(O) are shown
in Figure 10. The tube remained unchanged between
before and after the actual plant test. Dark-brown to black
scale was also observed at the same level as on the lowpressure drum inner surface. The amount of scale deposition increased approximately linearly after the water treatment system was changed, as shown in Figure 11. After
additionally considering the fact that no remarkable
change was observed in the scale deposition, we concluded that the new water treatment would maintain the
same scale deposition trend as that under the conventional treatment.
295
As shown in Figure 10, the surfaces of the low-pressure

turbine were also free of corrosion or other defects and
maintained nearly the same condition as under the conventional treatment system. Although the scale colors differ because of the difference in exposure time, they were
almost the same when viewed with the naked eye.
Benefits of Long-Term Operation with High AVT(O)
700
600
Thickness for shell

requirement = 4 mm
2007
2008
500
Frequency
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2011
400
300
200
As shown in Figure 12a, the thinning rate changed substantially between 2007 and 2008, verifying that wall thinning progressed during this period. However, since 2008,
when the traditional feedwater treatment was replaced
with high AVT(O), the wall thinning distribution profile has
remained almost unchanged, suggesting that this new
treatment system is effective for suppressing piping corrosion. As compared with the previous feedwater treatment,
the new treatment reduced the mean corrosion rate by
approximately 60 %, as shown in Figure 12b.
However, continuous thinning was observed in some of
the economizer tubes, probably because these tubes
were affected more severely by the flow environment than
by the feedwater itself.
100
0
3.5
4.0
4.5
5.0
5.5
Tube Wall Thickness [mm]
Figure 12a:
Wall thinning distribution at bottom tube nozzle stub of highpressure primary economizer (No. 1 panel right header).
Mean Wall Thinning Rate [m 1 000 h1 ]
High AVT(O) has been applied since 2008 up to now, and

measurement work is continuing to check the piping condition. As a typical example of the follow-up investigation
results, the change in the piping thickness in the highpressure economizer tubes of the No. 6 power plant in
Himeji No. 1 Power Station is discussed below. The feedwater temperature in the economizer tubes is about
160 C.
25
21.0
20
15
11.5
10
0
AVT(R)
High AVT(O)
Figure 12b:
CONCLUSIONS
The actual plant test of high AVT(O) has verified that this
new feedwater treatment reduces the iron concentration in
the system water more effectively than the conventional
treatment. Thus, the new method eliminates the need for
hydrazine injection and ensures that feedwater meets the
quality control criteria even during plant startup/shutdown. Inspection of major plant equipment also revealed
that introduction of the new feedwater treatment does not
affect their function or performance.
The actual plant test of high AVT(O) has verified that this
treatment provides an anti-corrosion effect equal to or
better than that of traditional treatments, while eliminating
the need for the use of hydrazine, which has adverse
health effects. In addition, prolonged use of high AVT(O) is
expected to suppress wall thinning due to FAC of carbon
steel tubes, thereby enhancing the integrity and economical efficiency of combined cycle power plants.
296
Comparison of mean thinning rates at tube bottom nozzle stub

of high-pressure primary economizer (No. 1 panel right-middle
header).
As described above, high AVT(O) is a superior water treatment that enhances the operation reliability of power
plants and saves on their running costs at little plant
upgrade expense. Through the introduction of high AVT(O)
into an actual plant, we have gained extensive technical
know-how on selecting plants that should be equipped
with the high AVT(O) and the water quality control method,
in addition to a great deal of knowledge about corrosion
protection methodology in a water environment.
Currently, high AVT(O) is applied to our 11 HRSGs, which
have 3 442 MW in total output. Moreover, in 2011, another
4 HRSGs overseas began high AVT(O) based on our proposal and detailed investigation for improving water
chemistry in the power plants.
REFERENCES
[1]
http://www.env.go.jp/en/chemi/prtr/prtr.html.
[2]
Kido, H., Ichihara, T., Tsubakizaki, S., PowerPlant

Chemistry 2011, 13(10), 623.
[3]
Water Conditioning for Boiler Feed Water and Boiler

Water, 2006. Japanese Standards Association,
Tokyo, Japan, JIS B 8223: 2006.
[4]
Bates, A. J., Bignold, G. J., Garbett, K., Middleton,

W. R., Penfold, D., Tittle, K., Woolsey, I. S., Nuclear
Energy 1986, 25(6), 361.
[5]
Suzuki, T., Asada, T., Kasahara, M., The Thermal and

Nuclear Power Generation Convention, 2008, 15, 1.
[6]
Asada, T., Suzuki, T., Yotsumoto, A., Isooka, T.,

Fukushima, F., The Thermal and Nuclear Power
Generation Convention 2009, 47, 1.
THE AUTHORS
Takashi Suzuki is a chemical engineer at the Engineering
Center of the Fossil Power Division at the Kansai Electric
Power Co., Inc. He has 25 years of experience in the field
of chemical engineering.
PPCHEM
desulfurization, and wastewater treatment plants at foreign power plants.

Kazumitsu Takanishi (M.S., Precision Engineering,
Osaka University, Osaka, Japan) is the general manager of
the Engineering Center of the Fossil Power Division at the
Kansai Electric Power Co., Inc. He has 25 years of experience in the field of chemical/mechanical engineering and
in construction projects for fossil power plants.
CONTACT
Tetsuo Yamamoto
Manager
Research & Development Group, Engineering Center,
Fossil Power Division
The Kansai Electric Power Co., Inc.
Sumitomo-Nakanoshima BLD, 2-18, Nakanoshima,
3-chome, Kita-ku
Osaka, 530-0005
JAPAN
E-mail: yamamoto.tetsuo@d5.kepco.co.jp
Tetsuo Yamamoto (M.S., Energy and Hydrocarbon

Chemistry, Kyoto University, Kyoto, Japan) is a manager
at the Engineering Center of the Fossil Power Division at
the Kansai Electric Power Co., Inc. He has 14 years of
experience in the field of chemical/mechanical engineering and in construction projects for fossil power plants.
Tetsuo Yamamoto also has experience with consultancy
services on construction/modification projects for boilers,
flue gas desulfurization, and wastewater treatment at foreign power plants.
Masanobu Maekawa is a chemical engineer at the Engineering Center of the Fossil Power Division at the Kansai
Electric Power Co., Inc. He has 15 years of experience in
the field of chemical engineering of fossil power plants.
Jun Hishida is an assistant manager at the Engineering
Center of the Fossil Power Division at the Kansai Electric
Power Co., Inc. He has 26 years of experience in the field
of chemical engineering of fossil power plants.
Satoshi Kuwano (M.S., Mechanical Engineering, Keio
University, Tokyo, Japan) is the deputy general manager of
the Engineering Center of the Fossil Power Division at the
Kansai Electric Power Co., Inc. He has 21 years of experience in the field of chemical/mechanical engineering and
in construction projects for fossil power plants. Satoshi
Kuwano also has experience with consultancy services on
construction/modification projects for boilers, flue gas
297
PPCHEM
Proceedings of the BIAPWS 2012 Symposium on Power

Plant Chemistry
Paul McCann and Mark Robson
ABSTRACT
The British and Irish Association for the Properties of Water and Steam held its annual Symposium on Power Plant
Chemistry on 2829 March 2012 in Chilwell, Nottingham. Summaries of the event proceedings are provided.
INTRODUCTION
The 14th Power Plant Chemistry Symposium, organised
by the British and Irish Association for the Properties of
Water and Steam (BIAPWS) and supported by the Royal
Society of Chemistry (RSC) Water Sciences Forum, was
held on 2829 March 2012 at the Village Hotel, Chilwell,
Nottingham. BIAPWS is the National Committee for the
UK and Ireland of the International Association for the
Properties of Water and Steam (IAPWS) and is also the
industry representative body for power plant chemistry.
The symposium consisted of two sessions: the first
session on 'Power Plant Chemistry Fundamentals' was
targeted at developing chemists and also engineers with
an interest in chemical operations and described the principles of cycle chemistry and boiler chemical cleaning.
The second session consisted of more detailed technical
presentations on 'Environmental and Water Treatment
Issues' and 'Power Plant Chemistry and Corrosion'.
This annual event continues to be very popular, with over
eighty delegates attending the first session and over one
hundred delegates attending the second session. This
demonstrated not only the continued interest in the UK in
developments in cycle chemistry and water treatment, but
also the interest in more fundamental aspects. The proceedings of the symposium are summarised in this report
(Figure 1).
BIAPWS AWARD
The annual BIAPWS award helps to support a university
student during a placement with one of the sponsoring
companies as a means of promoting awareness of the
topics of interest to BIAPWS and their industrial application and to provide a valuable opportunity for a student to
experience the industry. A number of past award winners
have since gone on to full time employment in power generation, demonstrating significant success for the award in
attracting high calibre individuals to the industry.
In 2011, the award recipient was David Docherty from
Imperial College, who spent ten weeks with EDF Energy
Nuclear Generation in Gloucester working on techniques
to access look-up tables for steam/water properties when
running computer simulations of transients in advanced
gas-cooled reactors (AGRs) (Figure 2). The results of the
study were presented at the symposium.
SYMPOSIUM PROCEEDINGS
Power Plant Chemistry Fundamentals
Power Plant Cycle Chemistry
Geoff Bignold, Consultant, and Mark Robson,
RWE npower
The presentation started with a clear and detailed examination of Pourbaix diagrams, how they are constructed
and their detailed application to corrosion in the water circuit. This was followed by a review of the various iron
oxides and how their stability and solubility control many
of the corrosion and deposition processes in the boiler.
The application of these fundamental processes led into a
discussion of the control of feed and boiler pH and that
controlling these to an alkaline pH minimises the corrosion
of iron alloys.
Various chemistry regimes for both feedwater and boiler
water were reviewed and included the use of either
ammonia or amines to control the pH in the feed water.
For boiler water, the use of sodium hydroxide (caustic
soda) or tri-sodium phosphate was detailed and the pros
and cons for each treatment were outlined.
298
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Figure 1:
Symposium proceedings.
Figure 2:
The BIAPWS Award presentation, showing from left to right, Paul McCann, BIAPWS chair, Andrew Bull, EDF Energy, David Docherty,
the BIAPWS Award recipient, Richard Harries, BIAPWS, and Andy Rudge, EDF Energy.
299
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Finally, the importance of steam purity was discussed with

the recognition that due to the very low solubility of the
majority of solutes in steam, in most cases well below the
steam quality limits, the principle controlling factor for
deposition in the steam turbine is kinetically driven and
not thermodynamics.
Boiler Chemical Cleaning

Bill Lawson, Alstom Thermal Services, Ray Clarke and
Geoff Darlow, ESB International, and Andrew Mosley and
Richard Geatrell, RWE npower
plant (CCGT) owned and operated by ESB International, a

comprehensive chemistry survey was carried out. The station has a triple pressure, vertically tubed, drum type HRSG,
with normal circuit operating pressures of high pressure
(HP) 116 bar, intermediate pressure (IP) 24 bar and low
pressure (LP) 4 bar. As the LP circuit includes a combined
LP drum/deaerator, an all-volatile feedwater treatment with
ammonia is used. The HP and IP boiler waters are dosed
with tri-sodium phosphate. No oxygen scavenger is dosed.
The purpose of the survey was to validate steam purity,
establish boiler drum carryover rates and to identify any evidence of phosphate hideout.
The reasons and justifications for chemically cleaning a

newly constructed boiler in preference to carrying out only
an alkaline flush and steam blow were detailed. The differences between a pre-operational and operational chemical clean were discussed and the rationale for deciding to
chemical clean was highlighted.
For the assessment, on-line ion chromatography was used

to measure the concentrations of sodium, phosphate,
chloride and sulphate in steam and boiler water during load
changes. Different chromatography systems were set up to
enable the measurement of concentrations in the g L1
range in steam and mg L1 range in boiler water.
For pre-operational chemical cleans, the impact on the

length of steam blows is important, though some manufacturers do not offer the chemical clean as a standard. It
is believed by most UK utilities that pre-operational
chemical cleans are beneficial in reducing the length of the
steam blows and forming a good protective oxide layer for
operation.
The survey showed that excellent steam purity is being

maintained at all times (Table 1). In the IP and LP steams,
the concentrations of salts were almost all less than
0.1 g L1 (though noting that the LP boiler water is not
dosed with phosphate). In the HP steam, concentrations
were slightly higher, but still only a maximum of
0.5 g kg1. This also confirmed the exceptional steam
after cation conductivities of < 0.1 S cm1 that are typically measured at the plant. From measurements of
sodium and phosphate in the HP and IP boiler waters and
saturated steams, carryover rates were calculated of
0.012 % for the HP drum and 0.008 % for the IP drum,
which are also extremely low.
The importance of achieving an iron and free acid plateau

during the chemical clean was outlined and, if this is not
achieved, the cause needs to be understood before progressing to the next stage of the clean.
With the larger modern design of heat recovery steam
generators (HRSGs), it was noted that it is important to
split the circuit up into a number of sections to achieve a
satisfactory clean. This needs to be supported by a
detailed method statement where valve operations and
cleaning steps are specified.
The importance of complying with safety and environmental requirements was highlighted by all speakers, and the
limitations this puts on hydrofluoric acid strength and
quantity to comply with COMAH regulation (Control of
Major Accident Hazards) requirements were discussed.
Power Plant Chemistry and Corrosion

A Chemistry Survey of the Steam/Water Circuit of a
Modern CCGT Power Station
Shauna Concannon, ESB International, and John Greene,
Consultant
In investigating phosphate hideout, sodium to phosphate

molar ratios were determined of 3.8 for the HP boiler water
and 3.0 for the IP boiler water. As the molar ratio of sodium
to phosphate should be 3.0 with tri-sodium phosphate,
this showed the presence of free sodium hydroxide in the
HP boiler water.
Mean Concentration [g kg1]
Steam Sample
Na
Cl
SO4
PO4
HP Saturated Steam
0.346
0.514
0.458
0.080
IP Saturated Steam
0.060
0.007
0.064
0.201
IP Superheated Steam
0.054
0.019
0.074
0.019
LP Saturated Steam
0.007
0.010
0.042
n.d.
LP Superheated Steam
0.074
0.006
0.049
n.d.
Table 1:
To fully understand the cycle chemistry performance and

behaviour at a modern 400 MW combined cycle gas turbine
300
Steam purity results.

n.d. not detected
In the LP steams, a slight increase in after cation conductivity was noted from 0.13 S cm1 in the saturated steam
to 0.21 S cm1 in the superheated steam. Ion chromatography measurements showed that this difference
was due to an increase in carbonate concentrations (i.e.
carbon dioxide), suggesting some degradation of organic
species across the LP superheater.
Breakdown of Organic Amines in AGR Steam/Water

Circuits
Andrew Bull, EDF Energy
Hartlepool is one of EDF Energy's fleet of advanced gascooled reactor (AGR) nuclear power stations in the UK. At
Hartlepool, the helical 'pod' boilers are of once-through
high pressure design with typical final steam conditions of
170 bar and 500540 C. The boilers must provide a high
level of reliability against tube leaks for nuclear safety reasons, whilst also lasting the lifetime of the station as their
design means that there is limited ability for inspection,
repair and replacement. Because of circuit design and
metallurgy, the cycle chemistry is based on ammonia allvolatile treatment with combined oxygen and hydrazine
dosing. However, magnetite deposition in the oncethrough evaporator stages has resulted in rising pressure
drops across the boilers. This has caused problems with
boiler instability, reduced generation due to feedwater
pressure limits and reduced steam temperatures, as well
as increased stress corrosion risks resulting from wetting
of austenitic superheater sections.
To counteract the increases in boiler pressure drop, the
use of an organic amine as a better high-temperature base
than ammonia was investigated to reduce magnetite solubility. Other potential chemistry options that were not suitable included the use of a fully oxygenated chemistry due
to the partial wetting of austenitic stainless steel superheaters and raising the pH with ammonia due to the effect
on the condensate polishing plant.
Following an evaluation of potential amine products,
dimethylamine (DMA) was selected for further trials due to
its basicity and limited predicted thermal degradation.
After initial test work with DMA at the Wythenshawe Boiler
Rig in Manchester proved successful, full scale plant trials
were carried out in Reactor 2 at Hartlepool from January
2011 onwards. An initial DMA concentration of 450 g L1
was dosed, which was increased progressively to the
desired target of 900 g L1.
Monitoring during the trial period showed that the average
rate of increase in boiler pressure drop was up to 2.6 times
lower with DMA dosing than with ammonia. Much of this
improvement coincided with a DMA dosed concentration
of half or two-thirds of the target concentration. Iron levels
in the feedwater system also reduced from around
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4 g L1 to less than 1 g L1, indicating that two-phase

flow-accelerated corrosion had been reduced in the balance of plant. There has been no evidence to date that
DMA dosing affects the operation or performance of the
condensate polishing plant.
During the trial, the percentage of DMA decomposing
decreased with time, possibly as a result of the surfaces
becoming conditioned. Analysis showed that the degradation products of DMA were methylamine, ammonia,
formic acid, carbon dioxide and neutral organic products
(probably methanol and formaldehyde). At the boiler outlet, formic acid levels of 40 g L1 were measured in
steam, which were significantly higher than expected,
though these also decreased with each operational
period. Due to the potential for formic acid to concentrate
in the early steam turbine condensate, additional assessment work was completed to demonstrate that the DMA
present maintains a sufficiently alkaline environment to
minimise the risk of stress corrosion cracking in the LP
turbine steels.
Corrosion Protection in Modern Power Plants

Brian Coles, Lake Technical Specialities
In the power industry, vapour phase corrosion inhibitors
(VpCIs) may be considered as an option to currently
established methods for plant and component preservation. To date, most power industry applications have been
for long-term gas side boiler preservation. VpCIs have
been used with some success in preventing corrosion
during shutdown periods at plants that have previously
had problems with environmental emissions when corrosion debris has been released from the stack during subsequent start ups.
VpCIs can be supplied in many types of carrier, including
water and oil. If chosen correctly, VpCIs can protect
vapour phases, liquid phases and liquid-vapour interfaces. When fogged into the boiler, they adsorb to metal
surfaces to form a mono-molecular layer that acts as a
barrier to oxygen and water. VpCIs can migrate up to three
metres from the point of application to protect recessed
areas and cavities. For long-term preservation, re-application is normally required within 23 years to minimise corrosion for the full period required. Badly fouled surfaces
require initial cleaning before the VpCI is applied. When
the boiler is re-started, VpCIs decompose at high temperature to oxides of carbon and nitrogen.
In the UK, VpCIs have been used successfully at CCGT
plants owned by Centrica to prevent gas side corrosion
during plant shutdowns. Examples include:
Peterborough Power Station
The station has had issues with rust particles being
301
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emitted from the HRSGs when they have been returned

to service after long and short outages. To try to prevent further occurrences, an HRSG was treated with
VpCIs after initial shutdown. At the end of the outage,
visual inspections confirmed that the tubes, fins and
other surfaces were free from corrosion, which was a
significant improvement in condition compared to previous outages. The unit was then returned to service
with no environmental problems reported. VpCIs are
now applied at the station at every planned unit outage.
South Humber Bank Power Station
The station has had problems with dew point deposition at the back end of the HRSG which has resulted in
boiler tube failures. Following experience at Peterborough, the HRSGs have been fogged with VpCIs
during outages. Since VpCI application started, the
number of similar tube failures has decreased.
Kings Lynn Power Station
VpCIs have been used to preserve the HRSG during an
extended shutdown and will be used for future plant
preservation.
Water side preservation may also be performed in either
wet or dry conditions using different VpCI chemicals,
though there has been much less practical experience
with this in power plant. The potential impact of residual
concentrations requires consideration.
Rapid Return of High-Accuracy Steam Properties for

AGR Thermal-Hydraulic Analysis
BIAPWS Award Lecture, David Docherty, Imperial College
David Docherty was the recipient of the 2011 BIAPWS
Student Award. As described, his work placement was
with EDF Energy Nuclear Generation investigating techniques to access look-up tables for steam/water properties
when running computer simulations of AGR transients.
The design of AGRs is such that, in most instances,
access for maintenance or addition of internal monitoring
instrumentation is not possible. Therefore, computer
simulations of plant performance are an extremely important part of the safety case. This project supported work
activities that aimed to produce fast access to the latest
steam/water properties routines to improve the speed and
accuracy of transient analysis.
The AGR plant modelling codes currently used by EDF
Energy can optionally obtain steam properties by direct
access to a previous release of the steam properties
formulation, IAPWS 84. However, as this already results in
relatively long simulation times, the use of the more accurate, but potentially much slower, IAPWS 95 release was
not deemed practical. Therefore, an alternative approach
was investigated to access IAPWS 95 in the form of look-
302
up tables. This approach is based on an in-house software

package initially developed some 20 years ago to generate look-up tables from previous steam properties polynomials. At that time, table interrogation was based on
two-dimensional bi-linear interpolation with routines
written in FORTRAN for general interpolation and also for
error checking.
To generate new IAPWS 95 look-up tables, both manual
and automatic approaches were investigated to develop
tables of all the properties to a specified accuracy. Initially,
the table mesh size was determined to provide a maximum error of 1 %. Manual tables were developed by running the IAPWS 95 routines, exporting the results, testing
the accuracy at each intermediate point and reducing the
mesh size in areas where the accuracy was not considered adequate. Automatic tables were generated by creating tables of a specified mesh size, using an error checking routine to evaluate their accuracy and then halving the
mesh size of the entire table if required.
Using these approaches, tables were successfully produced for all properties of water (not steam) with the
desired functionality and accuracy. Manual tables were
produced of variable mesh size, whilst the automatic table
routine produced tables of regular mesh size. Table interpolation proved to be around eight times faster than
running the IAPWS 95 code whilst remaining within the
required error tolerance.
Environmental and Water Treatment Issues

Severn Power Condensate Polishing Plant
Joe Woolley, Watercare International
Severn Power Station is a new 842 MW CCGT plant consisting of two single shaft combined cycle units. The
HRSGs are of triple pressure design with a once-through
HP circuit and drum type IP and LP circuits. The station
also has air-cooled condensers.
To maintain the feedwater purity required for the oncethrough HP stages, a condensate polishing plant was
specified to treat the full condensate flow of up to
440 m3 h1 in each generating unit. The treated condensate purity required was: conductivity 0.1 S cm1, total
iron 5 g L1, sodium 2 g L1 and silica 5 g L1.
As the feedwater would be conditioned with ammonia to
achieve a pH of 9.6, the polishing plant was also required
to operate in ammonia form to reduce the frequency of
regenerations. During the transition from hydrogen to
ammonia form operation, the sodium target was relaxed
to 10 g L1. In addition, the IP and LP drum blowdown
was to be recovered to the polishing plant for treatment to
optimise site water use.
To meet these requirements, the condensate polishing

plant supplied consisted of two units, each with a capacity of 440 m3 h1 and each consisting of two streams of
cartridge filters and mixed beds. In ammonia form, the
mixed beds were designed to achieve runs of up to 30
days (156 000 m3) between regenerations. To minimise
sodium slippage during conversion to ammonia form
operation, the mixed bed resins are regenerated externally
to separate the cation and anion resins as effectively as
possible. The regeneration system is common and consists of an initial resin separation vessel in which the resin
interface is retained, separate cation and anion regeneration vessels and a final mixing tank. The resins are transferred hydraulically between vessels and chemical regenerants are transferred by pumps. Depth cartridge filters
were provided for commissioning and replaced with
pleated cartridge filters for normal operation. Due to site
discharge restrictions, the ammoniated wastewater fraction from mixed bed regeneration is segregated and
tankered off-site for disposal.
At present, the polishing plant is performing within expectations and meeting design guarantees with blowdown
recovery. Mixed bed throughputs are around 150 000 m3
between regenerations. Treated condensate after cation
conductivity is 0.07 S cm1 during both hydrogen and
ammonia form operation. During the transition to ammonia form operation, some initial problems with resin separation contributed to sodium peaks of up to 10 g L1 in
the treated condensate. These issues were resolved
quickly and sodium concentrations in the treated condensate now peak at around 24 g L1, falling to
0.81.5 g L1 during normal operation in ammonia cycle.
By comparison, sodium concentrations in hydrogen form
operation are < 0.1 g L1. The percentage Na on cation
resin was found to be 0.030.05 % by the end of the
commissioning period, compared to up to 0.6 % when
there were problems with resin separation.
During commissioning, particles in the unfiltered condensate were found to be mainly within a size range of
25 m, with particle counts of 5002 500 per mL of
sample. After the pleated cartridge filters were installed,
particle counts were reduced to only 65234 per mL,
indicating effective removal. Although still early in the
operation of the system, later data showed that particle
counts in the unfiltered condensate had reduced to less
than 100300 per mL.
Troubleshooting Polishing Mixed Bed Systems

Brian Windsor and David Hayhurst, Purolite
This paper looked back at the historical problems that are
still being frequently encountered on polishing mixed
beds, these being typically apparent as very long rinse
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times to quality after regeneration, or consistently poor

treated water quality (high conductivity).
At all times, the treated water quality from a power plant
polishing mixed bed should have a conductivity between
0.060.10 S cm1, sodium < 10 g L1 and reactive
silica < 20 g L1. To achieve this, mixed beds should
never be run to exhaustion and the service cycle should
be stopped on time or throughput well before any increase
in conductivity or reactive silica. This premature regeneration adds little to plant operating costs.
If an issue is identified, a double regeneration is normally
recommended, during which operators should check that
resin levels and chemical regenerant quantities are correct
and that valve sequences and air blowers are working correctly. If this does not solve the issue and treated water
quality continues to be poor, this usually indicates one or a
combination of the following problems during regeneration (note that the points relate to in-situ regenerated
mixed beds, though most also apply to externally regenerated beds):
Poor resin separation
The density differences between modern cation and
anion resins mean that resin separation should be easily achieved. However, the resin interface must be
located in the correct position to prevent acid contaminating anion resin or sodium hydroxide contaminating
cation resin. If the interface is too low, the most likely
cause of this is loss of cation resin. If the interface is too
high, anion resin may be trapped in the cation layer,
usually caused by the backwash flow rate being too
low. If the backwash flow rate is too high, anion resin
can block the top strainer/collector and the flow rate
will fall. If the resin bed level is low, but the cation interface is in the correct position, anion resin has been lost,
either because the backwash rate may be too high or
resin has been lost due to damaged internals.
Inadequate slow (displacement) rinsing
At the end of a slow rinse stage, the conductivity of
water exiting the centre drain should be low, typically
significantly less than 100 S cm1, showing that the
regenerants have been washed from the bed. However,
over time, collection/distribution systems can become
blocked and flow rates and pressures will change,
which without adjusting plant settings means that
regenerants can be left in the system. This can be confirmed by checking the conductivity of samples at the
end of the rinse stage. Any problems can often easily
be addressed by extending the rinse time.
Poor drain down control before re-mixing
With modern resins, the re-mixing stage must work
perfectly to achieve a correctly mixed resin charge. To
achieve this, the water level should be only a few
centimetres above the top of the bed when starting the
303
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air mix. If the water level is below the top of the bed, the
air will not re-mix the resins. If the water level is too
high, the resins can start to separate again at the end of
the air mix stage, forming a cation layer at the bottom of
the vessel, from which small amounts of acid can be
released. Ideally, the mixed bed vessel should be
provided with a separate drain down valve from the
shell to enable the water level to be controlled exactly,
though this is often omitted in modern mixed bed
designs.
Air blowers
Poor bed mixing can be caused by problems with air
blowers, such as blower failures, loss of flow due to lifting relief valves or pipework leaks, or contamination of
the supply. There is also an increasing trend to use air
from station compressors rather than dedicated blowers, which can cause problems if the infrequent
demand for mixed bed resin mixing coincides with
other site demands.
Cooling Water Conditioning The Use of Scale Inhibitors across the French Fleet of Nuclear Power Plants
Philippa Lambert, EDF Energy
In France, EDF's operational nuclear power plant fleet
consists of 58 reactor units. Depending on location, plant
cooling is provided by either direct cooled (once-through)
systems using seawater or estuarine water (18 units),
direct cooled systems using river water (10 units), or recirculating tower cooled systems using river water (30 units).
In power station cooling systems, scale formation in condensers and cooling towers needs to be prevented to control health risks linked to the development of biofouling,
maintain unit efficiency, prevent load drops due to insufficient cooling and to reduce operating costs associated
with replacing fouled or corroded equipment, e.g., fouled
tower pack.
At the stations with tower cooled systems, the risk of scaling in the cooling circuits is site specific according to the
local river water quality and hydrogeology. The scaling risk
can also vary seasonally due to variations in water quality,
flows and temperatures. Most of the tower cooled
systems were designed to operate with high feed rates at
a concentration factor of only 1.5, with no initial cooling
water treatment. However, there have been a number of
important scaling events observed over time due to
changes in water quality, with concentrations of hardness
salts increasing. Therefore, company guidance for scaling
control has been improved and arrangements for scaling
control reviewed at each station.
To estimate the potential for scaling under different conditions, operating guidance has been developed for stations
304
that is based on the use of the Ryznar Stability Index. The

guidance defines acceptable operating areas, areas with
increased scaling risk and areas when the scaling risk is
sufficiently high that operational constraints may need to
be applied at the plant. To provide inputs for the index calculation, stations routinely monitor make-up water and
cooling water pH, calcium concentration, alkalinity, conductivity, temperature and cooling circuit concentration
factor. So that the calculation methodology and guidance
can be refined, the results are collected on a fleet-wide
database and compared to plant observations of scaling
(e.g., tower pack weights). To provide early warning of
potential scaling events, hydrogeological models are also
being developed with the aim of being able to predict the
water quality at a given site five days in advance.
Where cooling water chemical treatment is necessary for
scaling control, conditioning with sulphuric acid is used
most widely due to proven effectiveness, low cost and
limited environmental impact. At one site, hydrochloric
acid is used, whilst a number of sites use carbon dioxide,
which is effective in protecting the condenser, but not the
cooling tower, where it is stripped into the air flow. In the
future, most sites requiring chemical treatment will use
sulphuric acid instead of hydrochloric acid or carbon dioxide. Polymeric dispersants are currently used at only one
site, although there are plans to extend this to a second
site.
Mechanical curative measures being applied include
tower pack cleaning and replacement programmes and,
for condenser tubes, the use of mechanical Taprogge ball
cleaning systems. Ultrahigh pressure jet cleaning methods
are also being developed for condenser tubes.
Carbon Capture and Storage Overview

Tony Corless, Scottish Power
To maintain clean fossil fuels as part of a balanced and
sustainable energy portfolio, Scottish Power, part of the
Iberdrola Group, has completed extensive design and test
work on carbon capture and storage (CCS) technology.
Recently, a consortium comprising Scottish Power,
National Grid and Shell completed a detailed Front End
Engineering and Design (FEED) study of a commercial
scale CCS project at the existing 2 300 MW Longannet
coal-fired power station located in Fife, Scotland. This
was completed under the UK Government's competition
to build and operate a full-scale CCS system on power
generation, though a satisfactory subsequent deal to proceed with construction could not be met.
The project was based on capturing two million tonnes of
carbon dioxide a year from a 300 MW unit using postcombustion amine technology. The carbon dioxide would
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then be transported to the North

Sea by changing an already largely
existing gas pipeline before final
storage in a depleted gas reservoir
two kilometres below the sea bed
(Figure 3).
The key components of the capture plant included a direct contact
cooler to cool and polish the flue
gas, a carbon dioxide absorber
tower, a desorber and reboiler to
separate carbon dioxide from the
amine solution by heating, and a
reclaimer to separate impurities
from the amine solution. Following
the capture process, the carbon
dioxide would be pressurised,
deoxygenated and dried to meet
the pipeline specification.
Figure 3:
Schematic of proposed carbon capture and storage plant at Longannet (courtesy of
Scottish Power).
DCC
SPS
direct contact cooler

steam and power supply
To improve understanding of the

carbon capture process chemistry
and operating costs, Scottish Power also completed a
seven month trial of a 1 MW carbon capture unit at
Longannet in 2009. Most of the baseline testing used
monoethanolamine for carbon capture, though proprietary
amines were also tested. The choice of amine and amine
chemistry was critical for the process. As well as being
able to effectively capture carbon dioxide, important properties for future amine products must address safety, environmental acceptability, stability and energy efficiency,
where the amine regeneration must require as little energy
as possible.
Experience has shown that the process chemistry and
technology involved in CCS would work, though commercial incentives are less certain. Ultimately, an integrated
capture, storage and transport network for Europe is a
future possibility given the storage potential in the North
Sea.
worked on a range of topics within the chemistry group

investigating plant problems for 10 years. On leaving the
CEGB he carried out various chemistry-based R&D functions. In 2001, Mark Robson rejoined the power industry,
working with various companies until joining RWE npower
in 2008. Since rejoining the power industry he has been
responsible for plant chemistry and environmental issues,
working as a station chemist and more recently as a
chemistry and environment engineer in the corporate
engineering function of RWE npower.
CONTACTS
Paul McCann
E.ON New Build & Technology
Technology Centre
Ratcliffe on Soar
Nottingham NG11 0EE
England
THE AUTHORS
Paul McCann (M.S., Chemistry, University of Nottingham,
UK) is a specialist in power plant steam/water cycle chemistry, corrosion and water treatment at E.ON's New Build &
Technology global unit in the UK. He has over 12 years'
experience in the power industry, joining Powergen, subsequently E.ON, in 1999. Paul McCann is also the current
chair of the British and Irish Association for the Properties
of Water and Steam.
Mark Robson (Ph.D., University of Leeds, United Kingdom) joined the Central Electricity Generating Board
(CEGB) in the North East regional laboratories in 1980 and
E-mail: paul.mccann@eon.com
Mark Robson
RWE npower
Drax Business Park
PO Box 3
Selby
North Yorkshire YO8 8PQ
England
E-mail: mark.robson@RWEnpower.com
305
PPCHEM
Event
Events
This column contains information on conferences, workshops, meetings, etc.,

important for power plant chemistry. We intend to inform our readers about
events which will take place in the near future.
IEX 2012:
The
T
he Intern
International
national Ion Exchange
E
Conference
Confer
encce
19 - 21 Septe
September
mber 2012
Queens Col
College,
leege, University of C
Cambridge,
ambridge, UK
Organised
Or
ganised by SCIs
SCIs Separation
Separation Science
Science and
and Technology
Technology G
Group
roup
306
PPCHEM
Events
WEDNESDAY 19 SEPTEMBER
08:00
Registration and refreshments
08:45
Welcome and introduction

Michael Cox
09:00
Plenary Lecture (Chair: Michael Cox)

From the Donnan Membrane Principle to sustainable ion exchange processes and materials: a tribute
to Fred G. Donnan
A. K. SenGupta, Lehigh University, USA
10:00
Keynote Lecture (Chair: Michael Cox)

European regulatory requirements for synthetic, organic, ion exchangers and adsorbents in food
processing and potable water production
M-R. Diebold, Dow, Germany; C. Andersson, CEFIC, Belgium; G. Hamsen, Lanxess, Germany; V. Scilletta,
Resindion, Italy; B. Windsor, Purolite, UK
10:30
Refreshments
Session A
Session B
Water treatment (1)

Tribute to Prof Wolfgang Hoell
Chair: Brian Windsor
Bioprocessing
Chair: Sharon Williams
11:00
Temporary requirement for demineralised

water in large power stations, oil refineries
and other industrial sites
V. Skinner, Omobile, UK
Challenges for ion exchange chromatography in high

titre monoclonal antibody manufacturing processes
L. Allen, Lonza Biologics plc, UK
11:30
Shell-core ion exchange resin developments

W. Fries, Purolite, USA
Ion exchange as an integral part of antibody and nonantibody purification processes

W. Lewis, GlaxoSmithKline, UK
12:00
The regeneration efficiency of shallow shell

resins versus classical strong acid cations in
demineralisation process
C. M. Iesan and C. M. Bohdana, Purolite,
Romania; F. Boodoo, Purolite, USA;
A. M. S. Oancea, University Politechnica of
Burcharest, Romania
Applying ion exchange chromatography in biopharmaceutical protein purification

J. Liddell, FujiFilms Diosynth Biotechnology, UK
12:30
Production of high purity water from tap

water by electrodeionisation
O. Arar, U. Yuksel and N. Kabay, Ege University,
Turkey
Purification of PEGylated Proteins by Ion Exchange

Chromatography
E. Mueller, Tosoh Bioscience, Germany
13:30
Lunch
Water treatment (2)
Chair: K. Clive Thompson
Bioprocessing
Chair: Sharon Williams
14:00
Ionic transport selectivity in electrodeionisation

N. Emery, ELGA, UK
Title tba
Speaker tba
14:30
Selective ions rejection by nanofiltration

processes in potable water treatments
N. Pages and M. Reig, Polytechnic University of
Catalonia, Spain; A. Yaroshchuk, University of
Catalonia and ICREA, Spain; J. L. Cortina,
Polytechnic University of Catalonia and
CETAQUA, Spain
Chromatography fouling in the manufacture of vaccine

and therapeutic protein products
D. Bracewell, University College London, UK
307
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Events
Session A
Session B
15:00
Arsenic removal from groundwater by

adsorbents
J. Park, S. Shao, S. Nishihama and
K. Yoshizuka, University of Kitakyushu, Japan
Title tba
G. Eschbach, Merck Millipore, France
15:30
Batch and column studies for the removal of

Pb(II) using a weak acidic ion exchanger:
kinetics, equilibrium and breakthrough
curves
I. Vergili, G. Soltobaeva, Y. Kaya, Z. Beril
Gonder, S. Cavus and G. Grdag, Istanbul
University, Turkey
Title tba
Speaker tba, GE Healthcare
16:00
Developments in the control and design of

'Nitreat' Nitrate removal plants during
AMP4 and AMP5 at Anglian Water
P. Barratt, Anglian Water Services, UK and
R. Ingham, ACWA Services Ltd, UK
16:30
Refreshments
17:00
Poster session
18:00
Drinks reception
19:00
Dinner at Queens' College (non-residents please book in advance)
THURSDAY 20 SEPTEMBER
Session A
Session B
Nuclear applications
Chair: Sarah Price
Hydrometallurgy
Tribute to David Naden
Chair: Michael Cox
08:30
Resin use, specification and justification at

EDF
D. Mascarenhas, F. Gressier and S. Taunier, EDF,
France
Developments in the use of ion exchange in hydrometallurgy

M.H. Kotze, Mintek, South Africa
09:00
Sequestration resins for accelerating

removal of radioactive contaminants
P. L. Frattini, D. M. Wells and S. E. Garcia, EPRI,
USA; L. Yengoyan, San Jose State University,
USA; R. Asay and R. Kohlmann, Radiological
Solutions Inc., USA
Durability of ion exchange resins for the recovery of

uranium via resin-inpulp
T. Udayar, Z. Shange, M.H. Kotze and O. Yahorava,
Mintek, South Africa
09:30
The removal of cesium ion with natural itaya

zeolite and the ion exchange characteristics
M. Endo, N. Takizawa, E. Yoshikawa,
N. Muramatsu, T. Kawai and H. Unuma,
Yamagata University, Japan; A. Masano,
Y. Takeyama and T. Kahara, Zeeklite Co. Ltd,
Japan
Impact of silica on the adsorption and elution of

uranium
K. Soldenhoff, T. Safinski, M.T. Tran and S. Archer,
ANSTO, Australia
308
PPCHEM
Events
Session A
Session B
10:00
The assessment of possibility of use of

natural and modified aluminosilicates for
rehabilitation of radioactive contaminated
territories
A. V. Voronina, V. S. Semenischev, A .A. Bykov,
A. S. Kutergin, T. A. Nedobuh and
N. D. Betenekov, Ural Federal University, Russia
Molecular recognition technology separations of

metallurgical interest
N. E. Izatt, S. R. Izatt and R. L. Bruening, IBC Advanced
Technologies, USA
10:30
Cation exchange behaviour of hydrazine and

ammonia on electrically regenerated ion
exchange membranes and several polymeric
cation exchange resins
J. Greene, O. Cunningham and A. Hill-Wilson,
EDF Generation, UK
The hybrid correlation and its application to a nickel

resin-in-pulp circuit
B. McKevitt, P. Abbasi and D. Dreisinger, University of
British Columbia, Canada
11:00
Refreshments
Condensate polishing
Chair: Chris Bates
Catalysis
Chair: Kevin Blaxall
11:30
US BWR condensate polishing optimisation

S. E. Garcia, EPRI, USA; J. F. Giannelli and
M. L. Jarvis, Finetech Inc., USA
Synthesis of n-hexyl acetate in batch and continuous

chromatographic reactors using dual property based
gelular ion exchange resin catalyst
D. Patel and B. Saha, London South Bank University, UK
12:00
The effect of dimethylamine (DMA) on the

performance of condensate polishing plant
resins at Hartlepool Power Station
S. Price and C. Atkinson, EDF, UK
Liquid-phase alkylation of toluene with 1-hexene over

macroreticular ion-exchange resins
M. Cadenas, R. Bringu, C. Fit, M. Iborra, E. Ramrez and
F. Cunill, University of Barcelona, Spain
12:30
The performance of oil-fouled ion exchange

resin in the condensate polishing plant of
Dungeness B Power Station
S. Price, EDF, UK
Cleaner and efficient alkenes/terpenes epoxidation

process catalysed by novel polymersupported Mo(VI)
complexes
R. Mbeleck, M. L. Mohammed, K. Ambroziak and B. Saha,
London South Bank University, UK; D. C. Sherrington,
University of Strathclyde, UK
13:00
Lunch
Environment (1)
Chair: Nalan Kabay
Fundamentals (1)
Chair: Gary Foutch
14:00
Removal characteristics of M+-exchanged

acid clay (M = Li, Na and K) for toxic matter
S. Jun, M. Miyake, Y. Kameshima and
S. Nishimoto, Okayama University, Japan
Separation of electrolytes and organic solutes on

elastic ion exchange resins: modelling approaches
J. Heinonen, M. Laatikainen and T. Sainio, Lappeenranta
University of Technology, Finland
14:30
New sulfonated microcapsules containing

DEHPA for the selective removal of heavy
metals
. Alczar, A. de Lucas, M. Carmona and
J. F. Rodrguez, University of Castilla La
Mancha, Spain
Hydration of ion exchangers: thermodynamics and

quantum chemistry calculations
V. Soldatov, Institute of Physical Organic Chemistry of
NAS, Belarus and Lublin University, Poland; S. Pristavko
and V. Zelenkovskii, Institute of Physical Organic Chemistry of NAS, Belarus
15:00
Selection of the matrix and functional group

of the ion exchange resin in order to obtain
struvite under supersaturation conditions
M. A. Celaya, M. Ortueta, D. Muraviev and
F. Mijangos, University of the Basque Country,
Spain
Prediction of ion exchange equilibria with respect to

temperature for a ternary system of Na+-Ca2+-Mg2+
ions
M. Rustam and D. C. Shallcross, University of Melbourne,
Australia
309
PPCHEM
Session A
15:30
Events
Session B
Refreshments
Environment (2)
Chair: Kevin Blaxall
Fundamentals (2)
Chair: Vladimir Soldatov
16:00
Recycle use of hybrid process coupling ion

exchange with ultrafiltraton for boron
removal from geothermal water
N. Kabay, D. Yapici, P. Koseoglu and U. Yuksel,
Ege University, Turkey
Swelling of resins and sorbents in liquids and vapours:

thermodynamic paradoxes
V. A. Davankov and A. V. Pastukhov, Russian Academy of
Sciences, Russia
16:30
Development and characterisation of gel and

gel bead with SO3H groups for the removal of
Cu(II), Ni(II), Zn(II) and Fe(II) from metalcoating wastewater
S. Cavus, G. Ya ar, Y. Kaya, Z. Beril Gonder,
I. Vergili and G. Grdag, Istanbul University,
Turkey
Investigation of the mass transfer process in the metal

ion exchanger nanocomposites
T. Kravchenko, L. Polyanskiy, S. Khorolskaya and
A. Kalinitchev, Voronezh University, Russia
17:00
The extraction of mercury using a polymer

inclusion membrane containing Aliquat 336
J. M. Perera, P. Mornane, R. W. Cattrall and
S. D. Kolev, University of Melbourne, Australia
The main role of the hydrogen bond in the ion

transport processes of the cation exchangers
L.S. Nechaeva, E.V. Butyrskaya, V.A. Shaposhnik,
Voronezh University, Russia
17:30
Poster session
19:00
Gala dinner at Gonville and Caius College (please confirm attendance in advance)
FRIDAY 21 SEPTEMBER
Session A
Session B
Novel extractants (1)

Chair: Arup Sengupta
Biofuel
Chair: Klaus-Dieter Topp
09:00
Bifunctional ion exchangers: surface

modification of ion exchange materials with
metal nanoparticles
D. N. Muraviev, A. Alonso, J. Bastos-Arrieta,
M. Muoz and J. Macanas, Autonomous
University of Barcelona, Spain
Ion exchange resins catalysed esterification of free

fatty acids in used cooking oil with methanol: an
efficient pre-treatment method for biodiesel
production
B. Saha, London South Bank University, UK; S. Zainal
Abidin and K. F. Haigh, Loughborough University, UK
09:30
Bipolar nano-surface for high-performance

ion-exchange separation
A. Dolgonosov, R. Khamizov and N. Kolotilina,
Vernadsky Institute, Russia
New microporous polystyrene sulfonic acid catalyst

for free fatty acid esterification
D.R. Brown and E. Andrijanto, University of Huddersfield,
UK
10:00
Sulfonated carbon nanofibre fabrics for high

capacity ion-exchanger: size effect on
surface area, ion-exchange and adsorption
capacities
H. Matsumoto, S. Imaizumi, M. Minagawa and
A. Tanioka, Tokyo Institute of Technology, Japan
The role of ion exchange and adsorption on aqueous

and organic glycerol phase purification
M. Carmona, . Alczar, . Prez and J. F. Rodrguez,
University of Castilla La Mancha, Spain
10:30
Anion-exchange reaction of carbonate

layered double hydroxide in nonaqueous
system
T. Tanaka, Y. Kameshima, S. Nishimoto and
M. Miyake, Okayama University, Japan
Optimisation of recycling chromatography for biomass

hydrolysate fractionation using ion exchange resins
S. Hellstn and T. Sainio, Lappeenranta University of
Technology, Finland
310
PPCHEM
Events
Session A
11:00
Session B
Refreshments
Novel extractants (2)
Chair: Michael Cox
Adsorbents
Chair: tba
11:30
Selective separation of molybdenum by

highly functional xerogels enclosing LIX63
extractant
S. Susa, T. Sugimori, S. Masud Rana,
H. Mimura and Y. Niibori, Tohoku University,
Japan
Adsorptive recovery of some precious metals by

using microalgal waste after extracting biofuel
K. Khunathai, K. Inoue, H. Kawakita, K. Ohto, Saga
University, Japan; M. Kurata and K. Atsumi, DENSO
Corporation, Japan; S. Alam, Memorial University,
Canada
12:00
Adsorption properties of lanthanoids for

SiO2-P adsorbents impregnated with
extractants
K. Yamanishi, H. Mimura, Y. Sasaki, Y. Morita,
Tohoku University, Japan
Adsorptivity of irradiated polyvinylpolypyrrolidone to

metal ions
M. Nogami and N. Miyata, Kinki University, Japan;
N. Sato, Kyoto University, Japan
12:30
Selective adsorption and recovery of Au(III)

by alginate gel polymer microcapsules
enclosing TOA extractant
R. S. Masud, Tohoku University, Japan
Polystyrene-type matrices with ultimate crosslinking

densities
M. P. Tsyurupa, Z. K. Blinnikova, V. A. Davankov, Russian
Academy of Sciences, Russia
13:00
Award of prizes
13:15
Lunch and close

Source: http://www.soci.org/General-Pages/Display-Event?EventCode=SST075
we can't live without technical progress ...

... but don't forget the flowers
POWERPLANT CHEMISTRY
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P.O. Box 433
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Switzerland
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311
PPCHEM
The Long Road from Potatoes and Wood Shavings to

Combined Amine Mixtures
Albert Bursik
ABSTRACT
Although the use of organics in plant cycles has been a highly debated topic, there has been relatively little basic
research conducted on the influence of organics and their decomposition products on the plant components;
importantly, however, there is no scientifically based evidence to date that organics have caused serious availability
problems. After a brief overview of some of the many questions and open issues related to the application of organic
plant cycle treatment chemicals, this paper turns to its main theme, the history of the use of these additives and the
modern forms which are being used in steadily increasing numbers.
INTRODUCTION
There are not too many topics in power plant chemistry
that have been as controversially discussed as the role of
organics in plant cycles. Very often, this discussion has
not been fully objective and without bias, and it has often
lacked any research or detailed monitoring to support it.
Organics is a very general term. Different organic substances feature different properties and their behavior in a
plant cycle diverges greatly. The pressure and temperature
in the cycle, the residence time in the high-pressure/temperature part of the cycle, and this is very often disregarded the actual plant cycle chemistry (e.g., the oxygen
content in the cycle streams) have a major influence on
the decomposition of organics in the plant cycle.
Decomposition products may react among themselves or
with plant cycle materials; the latter may result in cycle
component corrosion.
It may be surprising to discover that the major reason for
the demonizing of organics during the last seven decades
has not been their behavior in the plant cycle, but rather
their behavior in the course of the makeup water treatment
for example, interactions between some organics and
ion exchange resins resulting in malfunction of the makeup water treatment systems. The novel water treatment
technologies based on the application of membranes, too,
may often suffer from organics-based problems; however,
they may also solve problems caused by organics present
in the organic-loaded raw water, for example when treating and recycling gray waters.
For many reasons, the use of organic plant cycle treatment chemicals has not been covered by the major plant
cycle chemistry guidelines. The fact is, however, that such
additives are being used in steadily increasing numbers
and not only in industrial steam generation. It is very
important to note that there is no scientifically based
evidence to date that organics have caused serious availability problems. This statement refers to both the natural
organics and organic plant cycle additives. Yes they
affect pH and cation conductivity but can they cause
failure? Or serious failure? These are the important questions that need answers from research first. In the feedwater, we need to know whether increased cation conductivity can affect corrosion of feedwater components
and/or flow-accelerated corrosion (FAC). In the drum
boiler water, do they affect the corrosion processes? What
about corrosion processes in the steam circuits? The
basic problem here is the production of liquids (which can
occur only during shutdown) and often organics have
been blamed. But we need some basic research here to
understand the processes. In the turbine, much work has
been done on the phase transition zone (PTZ) over the last
30 years, and we now have a very good understanding of
almost everything. However, none of this work has been
done on organic breakdown products or organics that do
not break down. What about shutdown and layup? Again
no basic research has been done and the vast majority of
organizations do not provide even basic shutdown protection. How do organics affect condensate polishing?
312
It is quite possible that the wording of this introduction will

remind you of the introductory paper presented at the last
(the second) International Conference on the Interaction of
Organics and Organic Cycle Treatment Chemicals with
Water, Steam and Materials of 2005. No wonder this
section is almost identical to the 2005 presentation [1].
At the Second International Conference on the Interaction
of Organics and Organic Plant Cycle Treatment Chemicals
with Water, Steam, and Materials, Mathews stated that the
concern over organic treatments is too often taken out of
the context of the potential and unknown risks, with perhaps too little focus on the benefits that some organic,
primarily amine, compounds may offer. We have not been
so critical, it would seem, of the counterpart inorganic
treatment chemicals. Acid phosphate attack, caustic
gouging, and caustic induced stress corrosion cracking
remain as major failure mechanisms, yet the use of NaOH
and Na3PO4 remain as the primary chemical treatment
regimes in fossil power plant boilers. Ammonia is often
touted has having insufficient "buffering" capacity to
prevent acid attack in the event of condenser leaks or to
prevent pH depression in first condensing steam while
remaining as the principal corrosive agent for copper
alloys; yet ammoniac treatment is the major feedwater
treatment in fossil and combined cycles, as well as in
numerous nuclear plants. We have become accustomed to
acceptance and management of the known risks of these
chemicals since they have redeeming benefits in controlling corrosion in the cycle. Perhaps organic treatment
chemicals have not been given the same consideration for
the benefits they offer because of the potential unknown
risks. It is very important to note that there is no scientifically based evidence to date that organics have caused
serious availability problems. This statement refers to both
the natural organics and organic plant cycle additives. Is it
likely that the unknown risks associated with the use and
degradation products of organic constituents will be any
greater than the underdeposit corrosion and stress corrosion cracking and other damage mechanisms experienced
with current inorganic treatment chemicals [2]?
It seems that there are still many questions and open
issues related to the application of organic plant cycle
treatment chemicals. However, they are not the subject of
this paper. In a brief overview, the history of organic plant
cycle treatment chemicals will be addressed.
PPCHEM
To answer this question, we have to go back to the first

century of our reckoning. Hero (or Heron) of Alexandria, an
ancient scientist living in Alexandria, published at that time
a well-known description of the first ever steam-powered
device, called an aeolipile [4]. What does an aeolipile, a
rocket-style jet engine which spins when heated, have in
common with plant cycle chemistry? Actually nothing it
is mentioned here only for one reason: it is the first
recorded device in which heated water produced steam
as the power source.
Some other famous inventors paved the way from this
ancient steam-powered device to the state-of-the-art
high-pressure plant cycle. There are for example:
Taqi al-Din Muhammad ibn Ma'ruf al-Shami al-Asadi,
who described the workings of a rudimentary steam
turbine in 1551 [5];
Giovanni Branca, who invented a rudimentary steam
turbine in 1629 [6];
Denis Papin, who built a model of a piston steam
engine in 1690 [7];
Thomas Savery in 1698 and Thomas Newcomen in
1712, who operated their atmospheric engines [7];
James Watt, who introduced a jet condenser to an
atmospheric engine in 1765 [7];
John Fitch, who built the first working model of a steam
rail locomotive in 1794 [8]; and
Richard Trevithick, who built the first full-scale working
railway steam locomotive in 1804 [8].
All operators of steam railways experienced unexpected
problems related to the water used for feeding the boilers
of locomotives. The concentration of water in the boiler (in
the first steam locomotive generation without condensate
return) resulted in scaling problems due to the precipitation of hardness in the boiler. This awkward situation could
be partially mitigated by the introduction of a condenser,
based, by the way, on the abovementioned work of James
Watt. This period was probably the dawn of plant cycle
chemistry. Adequate additives were sought to prevent
scale formation and, some time later, to prevent corrosion.
THE FIRST ORGANIC PLANT CYCLE ADDITIVES

THE HISTORY
The history of the use of organic additives in steam and
power generation is as old as steam generation itself [3].
This means that we first have to look back at the history of
steam generation. What was the first apparatus in which
water (and heat) was used to produce steam and who was
its inventor?
It is not generally known that the first plant cycle "additives," used mostly at sea, were potatoes and wood shavings. Potatoes were used to seal leaking boiler rolled joints
and wood shavings to seal condenser leaks. Later, more
sophisticated and as a rule multicomponent additives
came into operation. They still had some natural components like flaxseed, tannin, alginates (created from algae),
corn and potato starch, and colloidal graphite.
313
PPCHEM
Navy Compound 1933 is an example of the more sophisticated multicomponent additives of the 1930s. This product contained, according to a U.S. Navy standard [9,10],
47 % anhydrous disodium phosphate,
44 % soda ash, and
9 % corn starch.
For lack of time/space, the long road from potatoes and
wood shavings to combined amine mixtures has to be
shortened a bit. We want to forget the volumes of very
popular "snake oils" that typically have had more benefits
for the producers/sellers than for the user. Many of them
were not completely of organic nature and contained in
addition some inorganic components. The composition of
snake oils was as a rule unknown so that the user was
at the mercy of the supplier, who decided which product in
which concentration had to be used. The analytical methods to determine the content of the panacea were often
missing; the position of the user may be paraphrased as
flying blind without instruments. The sole exception was
the knowledge that the snake oil used contained about
90 % water. Considering these facts, this snake-oil period,
which a historian would call the Dark Ages, will skipped
here and the more scientific period will be dealt with.
systems. Chelants and dispersants are mostly used in

industrial systems operating at relatively low pressures.
Film-forming amines are increasingly being used in fossil
drum boiler units in industrial power and steam generation, in utilities up to high pressures, and in combined
cycles with heat recovery steam generators.
Neutralizing (Alkalizing) Amines

Thermal decomposition of hydrogen carbonate ions and
carbonate ions according to Eqs. (1) and (2), respectively,
results in the formation of carbon dioxide (CO2):
2HCO3 CO32 + CO2 + H2O
(1)
CO32 + H2O 2OH + CO2
(2)
The other source of CO2 present in the cycle may be

organic substances introduced into the cycle with suboptimal purified makeup or via cooling water inleakage in the
condenser. In industrial steam and power generation,
organics may ingress into the cycle with return condensate containing traces or even higher concentrations of
organic substances dealt with in the steam-supplied
industry.
MODERN ORGANIC PLANT CYCLE ADDITIVES

Organic-based products used for corrosion protection of
plant cycle components during transport and/or storage
may also enter into the plant cycle, in particular during the
commissioning of new units. These agents will be not
treated here. The focus is exclusively on organic additives
intentionally added to (injected into) the cycle to improve
(more or less) cycle chemistry, to reduce corrosion product generation and transport, and to avoid deposition in
the cycle. The possible secondary effects of the use of
organic additives are the extension of periods between
chemical cleans of the boiler, fewer boiler tube failures or
less steam pass damage, lower operating and maintenance costs, and an improvement in efficiency.
The organic plant cycle additives may be subdivided into
five categories although this partition does not fit all additives used. Many of the products available on the market
are multicomponent proprietary mixtures containing constituents of more than one of the following categories:
Neutralizing (alkalizing) amines,
oxygen scavengers,
chelants,
dispersants, and
film-forming amines.
As a rule, only chemicals from the first two groups have
been used in high-pressure fossil cycles and in nuclear
314
To neutralize carbon dioxide (and other possibly present

acidic contaminants), neutralizing (alkalizing) amines have
already been used, in particular in industrial steam and
power generation, for several decades. In many cases, the
amine of choice has been morpholine. The beginning of
the use of morpholine, and later of a mixture of morpholine
and cyclohexylamine (ratio 1:1), is dated to the late 1940s
[11]. According to [12], more than 40 % of the US nuclear
power plants with pressurized water reactors (PWRs) had
switched from ammonia to morpholine at the beginning of
the 1990s.
It has to be noted that for a long period, the Electric Power
Research Institute (EPRI) has been a leader with respect to
the selection and evaluation of amines that are potentially
applicable in the secondary cycles of PWR units. Cobble
and Turner presented and discussed a huge list of alternative amines starting with hydroxylamine and ending with
1,12-diaminodecane (all in all 77 potential candidates) in
1985 (Table 1) [12]. The qualification program of EPRI for
alternative amines with a better behavior than morpholine
was completed in 1992. The alternative amines tested
were ethanolamine, 5-aminopentanol, and dimethylamine
[13].
While there are many papers and reports dealing with the
application of alternative amines in secondary cycles of
PWR reactors, the reports about the use of these amines
in fossil cycles are not as common. Two older papers are
given as examples [14,15].
PPCHEM
H3NO
hydroxylamine
C4H11NO 2-aminobutanol
C6H15NO 5-methoxypentylamine
H4N2
hydrazine
C4H11NO 4-aminobutanol
C6H16N2
1,6-diaminohexane
CH5N
methylamine
C4H11NO 2-amino-2-methylpropanol
C7H13N
Quinuclidine
CH5N3
guanidine
C4H11NO N,N-dimethylethanolamine
C7H13NO 3-hydroxyquinuclidine
CH6N2
diaminomethane
C4H11NO 2-ethoxyethylenamine
C7H15N
heptamethyleneimine
C2H5N
aziridine
C4H11NO 3-methoxypropylamine
C7H17N
heptylamine
C2H7N
dimethylamine
C4H12N2
1,4-diaminobutane
C7H17NO 7-aminoheptanol
C2H7N
ethylamine
C5H11N
cyclopethylamine
C7H17NO 6-methoxyhexylamine
C5H11N
N-methylpyrrolidine
C7H18N2
1,7-diaminoheptane
C2H7NO ethanolamine
C2H8N2
ethylendiamine
C5H11N
piperidine
C8H19N
dibutylamine
C3H7N
azetidine
C5H13N
pentylamine
C8H19N
diisobutylamine
C3H9N
propylamine
C5H13N
isopentylamine
C8H19N
di-2-butylamine
C3H9N
2-propylamine
C5H13NO 5-aminopentanol
C8H19N
octylamine
C3H9N
trimethylamine
C5H13NO 2-(dimethylamino)propanol
C8H19NO 8-aminooctanol
C3H9NO 3-aminopropanol
C5H13NO 4-methoxybutylamine
C8H20N2
1,8-diaminooctane
C3H9NO 2-hydroxypropylamine
C5H14N2
1,5-diaminopentane
C9H21N
nonylamine
C3H9NO 2-methoxyethylamine
C6H13N
cyclohexylamine
C9H22N2
1,9-diaminononane
C3H10N2 1,3-diaminopropane
C6H13N
hexamethyleneimine
C10H19N
dicyclopentylamine
pyrrolidine
C6H13N
N-methylpiperidine
C10H23N
decylamine
C4H9NO morpholine
C6H15N
dipropylamine
C10H23N
diisopentylamine
C4H10N2 piperazine
C6H15N
diisopropylamine
C10H24N2 1,10-diaminodecane
C4H11N
butylamine
C6H15N
hexylamine
C11H25N
C4H11N
isobutylamine
C6H15N
triethylamine
C11H26N2 1,11-diaminoundecane
C4H11N
2-butylamine
C6H15NO 6-aminohexanol
C12H23N
dicyclohexylamine
C4H11N
t-butylamine
C6H15NO N,N-diethylethanolamine
C12H27N
dodecylamine
C4H11N
diethylamine
C6H15NO 2-(dimethylamino)-2-methylpropanol
C12H28N2 1,12-diaminodecane
C4H9N
undecylamine
Table 1:
Organic bases considered in investigations of most promising substances for use as pH control agents in steam generator and
auxiliary hot water systems.
What have been the reasons for the search for and the use
of neutralizing (alkalizing) amines in both nuclear and
fossil power generation? The reasons are nearly identical:
the amines are used as a remedy to problems caused by
inadequate materials selection or inadequate design of
major plant cycle components. Under this heading belong
both corrosion product generation and transport into the
steam generators of PWR reactors and corrosion issues in
industrial plant cycles, often with very mixed metallurgy
and a complicated design of heat recovery components,
which very often differ from classic steam generators.
In contrast to nuclear power generation, in fossil cycles

many multicomponent proprietary mixtures of amines
(combined to some extent with oxygen scavengers) are
applied. They are sold with labeling that does not including any meaningful information about the individual components. Some information may be extracted from the
particular material safety data although it does not contain
all the components and has only approximate data about
the actual concentration of the component listed. For this
reason, an appropriate evaluation of the additive concentration is not very easy.
315
PPCHEM
It is a matter of fact that most organic compounds are not

completely stable under typical plant cycle pressure and
temperature conditions even if some organic compounds
may be considered as persistent [16]. Naturally, when discussing the behavior of organics within the cycle, the
mean residence time in areas with the highest temperature
is of particular importance.
It is very difficult to predict the effects of decomposition
products of organics on the cycle pH. A very small amount
of decomposition products may markedly affect (i.e.,
lower) the pH in critical cycle areas where the first condensate is formed (heaters, steam turbine). The decomposition products of organic matter may be, for example,
smaller neutral compounds that are easily removed via
deaeration in the condenser or deaerator, low-molecular
weight organic acids, and carbon dioxide. In the case of
heteroatom-containing organic compounds, strong inorganic acids are the probable decomposition products.
Adequate organic alkalizing agents are capable of alkalizing their own decomposition products even in the phase
transition zone (PTZ) in the turbine [1].
Unfortunately, some inadequate organic treatment chemicals available on the market are still not sufficiently stable
at the temperatures and pressures encountered in fossil
plant cycles. Their decomposition products create dangerous low-pH conditions in the area of the beginning
condensation, e.g., in the PTZ of the turbines or on the
steam/condensate side of feedwater heaters [1].
Reports about the early application of the abovementioned scavengers include among others the following
references: carbohydrazide [20,21], hydrochinone [15],
N,N-diethylhydroxylamine [20,22], methyl ethyl ketoxime
[2325], erythorbic acid (ammonia neutralized) [26], N-isopropylamine [27], and ascorbic acid [28].
Generally, it should be noted that hydrazine substitutes
have commonly been used in fossil plants, in particular in
industrial power generation; their use in nuclear power
plants has been very rare and limited to auxiliary systems
and for layup purposes (see for example [2932]).
Chelants
Chelants were introduced in the feedwater and boiler
water treatment in the early 1960s [33,34]. Two chelants
have typically been used: ethylenediaminetetraacetic acid
(EDTA) and nitrilotriacetic acid (NTA), or rather their
sodium or ammonium salts. Chelants form complexes
with calcium and magnesium ions; these complexes are
soluble. Due to the possible thermal breakdown of organic
molecules at higher temperatures, the use of chelants is
limited to boilers operating at pressures lower than
100 bar [35].
By the way, EDTA and NTA salts have also been used for
the chemical cleaning of boilers [36,37].
Dispersants
Oxygen Scavengers
Since the first report of Zimmermann [17], hydrazine has
been the chemical of choice for deoxygenation in plant
cycles of fossil and nuclear power plants. Although
hydrazine can be applied safely without any effects on
human health or the environment [18,19], there has been
an increasing pressure on the part of authorities to abstain
from hydrazine use.
Organic oxygen scavengers, often called hydrazine substitutes, are, for example,
carbohydrazide (1,3-diaminourea)
hydrochinone (1,4-benzenediol)
N,N-diethylhydroxylamine
methyl ethyl ketoxime (2-butanone oxime)
erythorbic acid (2-(1,2-dihydroxyethyl)-4,5-dihydroxyfuran-3-one).
N-isopropylamine
ascorbic acid ((5R)-[(1S)-1,2-dihydroxyethyl]-3,4-dihydroxyfuran-2(5H)-one)
316
Lignin, tannin, and starches, used as dispersants for many

decades, were replaced by synthetic polymers in the
1980s. The new polymers are composed of acrylic acid,
methacrylic acid, acrylamide, maleic acid, and sulfonated
styrene subunits, and are either homopolymers or copolymers of varying compositions [38]. Dispersants are often
used in multicomponent proprietary mixtures, also in combination with phosphates or phosphonates.
Film-Forming Amines
Despite the fact that the use of organic cycle treatment
chemicals is not advised in any major international cycle
chemistry guideline, many variations of the amine treatment have been used for decades in industrial steam and
power generation. In the last two decades, film-forming
amines have become the most important organic additive;
the extent of amine treatment use in fossil power plants
has been increasing [39]. Film-forming amines represent a
relatively new group of organic plant cycle treatment
chemicals and are used mostly as components in proprietary amine mixtures, which may also contain neutralizing
(alkalizing) amines and sometimes an oxygen scavenger.
Film-forming amines are defined as chemical substances

from the family of the oligoalkylamino fatty amines and
can be characterized with the general chemical formula
R1-(NH-R2-)n-NH2, where n represents a whole number
between 0 and 7, R1 an unbranched alkyl chain with 12 to
18 carbon atoms (fatty alkyl chain), and R2 a short-chain
alkyl group with 1 to 4 carbon atoms. The simplest representative is the well-known octadecylamine (n = 0, R1 =
C18H37) [40].
The film-forming amines may be divided into two subgroups aliphatic monoamines and polyamines. The
typical representative of aliphatic monoamines is octadecylamine, and of polyamines oleyl propylene diamine or
stearyl dipropylene triamine [40].
Aliphatic Monoamines
In 1946, Kahler [41] filed a
patent describing for the first time the use of film-forming
amines for corrosion protection. Since this date, filmforming monoamines, in particular octadecylamine, have
been used at fossil power generators with low operating
pressures, and in high-pressure cycles predominantly for
corrosion protection during standby and layup. Another
application reported is for corrosion protection in large
district heating systems although this use has not been
without deposition problems.
Of the older interesting papers dealing with the use of
octadecylamine, the paper authored by Akol'zin et al. [42]
and Akol'zin's book [43] have to be mentioned. According
to [44], film-forming amines like octadecylamine and
dodecylamine have been used in WWER plants with success. Reports by Filippov et al. [45,46], Avdeev et al. [47]
and Kukushkin et al. [48] confirm that octadecylamine has
been used in secondary cycles of Russian pressurized
water reactors (VVER-440) although the typical usage is
for corrosion protection during shutdown and layup.
Polyamines
The use of polyamines may be traced
back to the work of Moran [49]. Although polyamines have
been successfully used to a large extent in industrial and
utility power generation (see [50] for examples), research
work on polyamines has not been very comprehensive
although the exceptions prove the rule. Among these
exceptions is the work reported by Bohnsack [51], Frahne
and Bloom [52,53] and by Ochoa et al. [54], although the
last paper focuses on the application of polyamines in
cooling circuits.
It is highly appreciated that in recent years publications
dealing with research results related to the application of
polyamines have been appearing more frequently [5558].
PPCHEM
ORGANIC TREATMENT CHEMICALS CURRENT

STATE
Organic treatment chemicals are widely talked about;
news of positive experiences with these chemicals has
spread rapidly (some examples only):
operators of nuclear power plants with pressurized
water reactors have achieved success with advanced
amines applied in secondary cycles and are thinking
about (or are already testing) the use of other organic
chemicals as dispersants for deposition control and of
film-forming amines for corrosion protection during
shutdown;
operators of fossil drum boiler units with operating
pressures equal to or below 100 bar have used many
proprietary amine-based mixtures with or without dispersants and have markedly reduced corrosion and
corrosion product transport, also in the very complicated systems typical for industrial steam and power
generation;
film-forming amines are increasingly being used in the
industry and recently also in high-pressure drum boiler
units in utilities. In units operated with film-forming
amines, the state of the steam turbines is excellent (no
deposition, no corrosion);
there has not been any irrefutable evidence that organics and/or organic breakdown products are directly
involved in boiler tube failures or steam path damage.
There are some open issues which need further investigation, e.g., the impact of organic treatment chemicals on
ion exchangers in condensate polishing plants and the
possible interference by organic treatment chemicals or
their decomposition products with the standard cycle
chemistry monitoring instrumentation. However, the
biggest barrier impeding the broader use of these chemicals is the fact that no internationally renowned fossil
cycle chemistry guidelines adequately cover the use of
organic plant cycle treatment chemicals in fossil plant
cycles.
It seems that as has been the case with many other plant
cycle treatments, e.g., with the oxygenated treatment
the researchers are arriving late at the scene, trying to
explain why and how these chemicals, which have already
been proven to work many times under practical conditions, actually function. And, the organizations issuing the
cycle chemistry guidelines are lagging behind even more.
It is believed that there is actually a niche for the amine
treatment (with the preference for the polyamine/amine
treatment) in the continuum of treatments. For the
polymine/amine treatment, the possible niche might be
placed in the open edge of the funnel of the continuum of
treatments. In this case, the Dooley's diagram [59] will
317
PPCHEM
look something like Figure 1 [60]. This may surprise the

"purists" among plant cycle chemists. It is absolutely possible that the introduction of optimum organic additives
into the high-pressure cycles with drum boilers and in
combined cycles with heat recovery steam generators will

represent a similarly important step as the introduction of
the oxygenated treatment to plant cycles with oncethrough steam generators.
No Condensate Polisher
Seawater Cooled
High TDS
Cooling Tower
Level of Possible/Probable Impurities.

Ability to Neutralize/Buffer Contaminants
Continuum of Treatments
Be
a
-Le
r In rol
i
r A nt
tte Co
ka
ge
Condensate Polisher
or Tight Condenser
CT
Amine/Polyamine Treatment
PC(L)
AVT(O)
PC
PC(H)
AVT(R)
OT
All-Ferrous Metallurgy
Can Be Mixed-Metallurgy or All-Ferrous

Possible Operational Problems
(Hideout, Hideout Return, Steam Limits)
Increasing Need for High Purity

Increasing Ease of Operation
Probability of Better Performance
(Availability Loss, Fewer Chemical Cleans)
Figure 1:
Amine treatment as part of the continuum of treatments state-of-the-art amines (adapted from [59]).
CT
PC(L)
PC
PC(H)
AVT(O)
AVT(R)
OT
caustic treatment
phosphate treatment with lower levels of phosphate
phosphate continuum
phosphate treatment with higher levels of phosphate
oxidizing all-volatile treatment
reducing all-volatile treatment
oxygenated treatment
ACKNOWLEDGMENT
REFERENCES
The author thanks Roy van Lier (SABIC Europe B.V.,

Geleen, Netherlands) and Sergej Jur'evi Suslov (AllRussian Thermal Engineering Institute, VTI, Moscow,
Russia) for their help in the search for older literature.
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PPCHEM
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PPCHEM
THE AUTHORS
Albert Bursik (Ph.D., Mechanical Engineering, University
of Stuttgart, Germany, Chemical Engineering, Institute of
Chemistry and Chemical Technology in Prague, Czech
Republic) worked for over 35 years as a chemist in several
utilities. Albert Bursik is an Honorary Fellow of the
International Association for the Properties of Water and
Steam, and has published more than 200 scientific and
technical publications. He is an associate professor at the
University of Stuttgart, an internationally active consultant
specialized in troubleshooting in fossil power plants, and
works as the editor of the PowerPlant Chemistry journal.
CONTACT
Albert Bursik
PowerPlant Chemistry GmbH
P.O. Box 1269
68806 Neulussheim
Germany
E-mail: editor@ppchem.net
Chemists and engineers from fossil and nuclear power plants and from industrial power generation, vendors,
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PPCHEM
Events
A PPowerChem
API
owerChem
m 2012
PPower
ower Station
Station CChemistry
hemisstry Conference,
Confference, Exhibition
Exhhibition and Training
Trainingg CCourses
ourses
Sunday 27thh May
Sunday
May ttoo FFriday
riday 1st June
Juune
TThe
he Crowne
Crowne Plaza Terrigal,
Terrigal, NSW
GGold
old SSponsor
ponsor
SSilver
ilver SSponsor
ponsor
OOrganising
rganising Committee
Committee
Photos
Phot
os courtesy
courtesy of AAurecon,
urecon, DDelta
elta EElectricity,
lectricity, EEraring
raring Energy
Energy & Crowne
Crowne Plaza TTerrigal
errigal
Reinforcing
Reinf
forrcing the importance
imporrtance of PPower
owerr Sta
Station
tion Chemistry
Chem
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322
PPCHEM
Events
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your fello
w dele
gates for a social rround
ound of golf
ee off tim
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mes will be frfrom
om 1pm aatt Shell
each GGolf
o CClub.
olf
lub.
G o l f : Join your
fellow
delegates
golf.f.. TTee
Shellyy BBeach
Welcome Reception
W
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eption: TTrivia
rivia Nigh
NNightt
Welcome
Reception:
TTime:
ime: 7:00 pm - 10:00 pm
LLocation:
ocation: Seasalt
Seasalt LLower
ower RRoom
oom
m
DDress
ress code:
code: CCasual
asual
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Inclusive for cconference
onference delega
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tes,
additional guests: $90.00
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Whats
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LLook!
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irate ship ccoming
o
oming
ttoo plunder
shores
ship,, LLord
Ashley,, trtrying
the fair shor
es of TTerrigal
errigall or just the ghost ship
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of fun and frfrivolity
ivolity aatt the
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aditional PPub
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eassalt LLower
ower rroom,
oom,
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May.y.
on Sunda
history
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mayhem
DDrawing
rawing frfrom
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ory of ship
wrecks and mar
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yhem from
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theyll
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nightt
acr
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eass, who kknows
nows wha
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h t tack they
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f e, ther
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of men
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INTERNATIONAL LIMITED
Day 1 Monday 28th

8:00
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Registration
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Welcome
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elcome an
andd opening rremarks
emarks
Mike
M
ike GGriffin,
riffi
ffin, CChief
hief Ex
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fficer
TThe
he AAustralian
ustralian PPower
ower Institut
Institutee
9:00
KKeynote
eynote SSpeaker:
peeaker: OOptimizing
ptimizing the CContinuum
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o CCycle
ycle
Chemistry
Ch
Chemistr
ity
JJim
im Ma
Mathews,
thhews, PProgram
rogram Manager - BBoiler
oiler & TTurbine
urbinne SSteam
team
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heemistry PProgram
rogram
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9:35
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reventing sstandstill ccorrosion
orrosion on LP turbines thr
tthrough
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shut
down
optimised sh
hut do
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FFrank
rank Udoo LLeidich,
eidich, HHead
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AAlstom
lstom PPower
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ystems, GGermany
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area
10:00
Morning TTea
eaa - EExhibition
xhibition ar
ea
latest
chemistry,
air-cooled
10:25
TThe
he la
test onn chemistr
y, ccorrosion
orrosion and FFAC
AC in ai
ir-cooled
ccondensers
ondensers ((ACC)
ACC)
BBarry
arry DDooley,
oooley, SSenior
enior Associa
te
Associate
SStructural
tructurall In
tegrity Associa
tes Inc
Integrity
Associates
Inc.,., USA
10:55
Unit outage in
ternal inspec
tions ffor
or FFAC
AC aatt Stan
nwell
internal
inspections
Stanwell
PPower
ower Sta
tioon
Station
BBrett
rett CConnor,
onnnorr, SStation
tation CChemist
hemist
SStanwell
tanwell CCorporation
orporation
11:20
CCopper
opper
pp tr
ansspor
p tation aatt Eraring
Eraringg PPower
ower Sta
tionn
transportation
Station
Mark W
ybburn, Asset CChemical
hemical TTeam
eam LLeader
eader
Wyburn,
EEraring
raring PPower
ower SStation
tation
11:45
FFAC
AC M
anageement in CS EEnergy
nergy ccovering
overing Callidee BB,, Callide C
Management
and KKogan
ogan CCr
eek PPower
ower Sta
tions
Creek
Stations
GGary
ary Jo
hemistry
Joy,y, Manager CChemistry
CS EEnergy
nergyy
12:10
QQuestions
uestions
12:20
LLunch
unch - EExhibition
xhibition ar
ea
area
SESSION
SE
SSION 2
1:20
1:45
2:10
2:35
Degassed ccation
Degassed
ation cconductivity,
onductivity, a side bbyy side ccomparison
omparison
of th
he rreboiled
eboiled and nitr
ogen spar
ger m
methods in a CCCC unit
the
nitrogen
sparger
John PPowalisz,
owalisz, DDirector
irector of Sales Asia andd LLatin
atin AAmerica
merica
SSentry
entry EEquipment
quipment CCorporation,
orporation, USA
FFailure
ailuure in
vestigation of a leaking
leaking titanium-tube
um-tube ccondenser
ondenser
investigation
M
Mor
risi YYoung,
oung, PProfessional
rofessional
f i l EEngineer
ngineer
i ((Chemistry)
Che
hemistr
i t y))
Morris
CContact
ontact EEnergy
nergy
SSelecting
eleecting ffeedwater
eedwater hea
ter tube ma
terials
e
ffor
or gr
eater
heater
materials
greater
effic
ciency and reliability
reliability
efficiency
DDan
an JJanikowski,
anikowski, TTechnical
echnical Manager
Pl
ymouth TTube
ube CCo.,
o., USA
Plymouth
W
ater
e st
eam ccycle
ycle chemistr
oring aand organic
organic additiv
ves
es
Water
steam
chemistryy monit
monitoring
additives
Mar
co LLendi,
endi, TTechnical
echnical SServices
ervices Manage
Marco
Managerr
SW
AN AAnalytical,
nalytical, SSwitzerland
witzerland
SWAN
QQuestions
ueestions
AAfternoon
fternoon
e
TTea
ea - EExhibition
xhibition ar
ea
area
3:00
3:10
SE
SSION 3
SESSION
3:30
Erarring PPower
ower Sta
tion - Star
t-up, shut down,
down, lay-up
lay-up
Eraring
Station
Start-up,
imp
rovements - PPart
art 1
improvements
EElise
lise RRing,
ing, EEfficiency
fficiency EEngineer
ngineer
EEraring
raring PPower
ower SStation
tation
3:55
EEraring
rarring PPower
ower Sta
tion - Star
t-up, shut down,
down, lay-up
lay-up
Station
Start-up,
iimprovements
imp
rovements
t - PPart
art 2
NNatasha
atasha CCudmore,
udmore, CChemical
hemical Plan
wneer
Plantt OOwner
EEraring
raring PPower
ower SStation
tation
4:20
A ne
ew appr
oach ttoo chemistr
allourn
new
approach
chemistryy alarms aatt YYallourn
FFranz
ranz SStoffel,
toffel, CChemical
hemical EEngineer
ngineer
TRUener
gy Yallour
YYallourn
allourn
TRUenergy
4:45
QQuestions
ueestions
4:55
IIAPWS
APWS
WS and the FFormation
ormation of an AAustralian
ustraliann NNational
ational CCommittee
ommittee
GGary
ary Jo
hemistry, CS EEnergy
nergyy
Joy,y, Manager CChemistry,
5:10
CClose
losee of DDay
ay one
(Program
(P
rogram subjec
subjectt ttoo change)
Monday 28th: Conference Dinner

Veolia
Water
invites
Veolia W
ater SSolutions
olutions & TTechnologies
echnologies in
vites yyou
ou ttoo the API PPowerChem
owerChem CConference
onference DDinner
inner held aatt the HHenry
enry KKendall
endall BBallroom
allroom
Proudly
Water
Proudly Sponsored
Sponsored bby:y: VVeolia
eolia W
ater SSolutions
olutions & TTechnologies
echnoloogies
Time:
Inclusive
delegates,
Time: 7:00 pm - 11:000 pm Dress
Dress code:
code: Smart
Smart Casual
Casual CCost:
ost: Inclu
sive for cconference
onference delega
tes, additional guests:
ests: $135.00
www
w.. a p i . e d uu.. a u
A P I Powe r Ch e m 2 0 1 2 CCo n f e re n ce, E x h i b i t i o n a n d Tra i n i n g Co u r s e s 2
323
PPCHEM
Events
D ay 2 Tu e s d ay 2 9 t h
SESSION
SE
SSION 4
9:00
KKeynote
eynote AAddress:
dddress: HRSG Chemistry
Chemistry
Barry
Associate
Barry Dooley,
Senior Associa
te
Doooley, Senior
Structural
Structural Integrity
Integrity Associates,
Associates, Inc.
Inc. USA
2:15
EExperience
xpeerience fr
from
om post-combustion
post-combustion ccapture
aptture pilot plan
plantt
oper
operations
rations
i in AAustralia
ustralia
li
Mrr Aaron
M
Aaron Cottrell,
Cottrell, RResearch
esearch TTeam
eam LLeader
eader
CSIRO Energy
Energy Technology
Technology
9:35
Approach
chemistryy ffor
Appr
oach ttoo select
or the
select the right
right chemistr
plant
individual pl
lant
Michael
Michael Rziha,
R Head
Head of Department
Department Power
Power Plant
Plant Chemistry
Chemistry
Siemens,
Siemens, Germany
Germany
2:40
Algae
production
Alga
ae pr
oduction using CO2
CO2 emissions trial
Nerida
Nerida Airs,
Water Managemen
Managementt Speciali
Specialistst
Airs, Water
Tarong
Tarong Power
Power SStation
tation
10:05
chemist/chemical
trouble
TThe
he role
al engineer for
ouble
role of the
thhe chemist/chemic
for
o the
t tr
free
fr
ee operation
operatioon of thermal plants
plants with heat
heat rrecovery
ecovery
steam
st
eam generators
generrators
David
David Addison,
Adddison, Principal
Principal
Thermal
Thermal Chemistry
Chemistry Limited,
Limited, NNew
ew Zealand
Zealand
3:05
Questions/Panel
Questions/Panel
3:15
Afternoon
Tea
area
Afternoon
e
Tea - EExhibition
xhibition ar
ea
10:30
Morning Tea
Teaa - Exhibition
Exhibition area
area
10:55
11:45
treatment
NNeutralizing
eutralizingg amines versus
versus ammonia in the tr
e tment of
ea
purityy bolier
high purit
b
Wah-Hing
Wah-Hingg Siong,
Siong, Regional
Regional Technical
Technical Manager
GE Water
Malaysia
Water & Process
Process Technologies,
Technologgies, Mala
yysia
IIntelligent
ntelligent sensor
sensor management
management
Alni
Alni Tatari,
Tatari, Business
Business Development
Development Manager
Mettler TToledo
iPAC
o - iP
oledo
AC Soultions
Soultions
QQuestions
uestions
11:55
PPanel
anel discussion
discusssion 1 (cycle/HRSG)
(cycle/HRSG)
12:40
area
LLunch
unch - Exhibition
Exhibition ar
ea
11:20
SESSION
SE
SSION 5
1:40
KKeynote
eynote AAddress:
dddress: Australian
Australian application
application of low
low emission
ccoal
oal technologies
technologies and the Callide OOxyfuel
xyfuel PProject
rojeect
Terry
Terry Wall,
Wall
Wall, PProfessor
rofessor
University
University of Newcastle
Newcastle
SESSION
SE
SSION 6
Performance
demineralisation
plantt ion eexchange
3:35
Performance of deminer
alisation plan
xchange
resins
chlorinated
resinns when contaminated
contaminated with high chlorina
orinated ffeedwater
eedwater
Tony
Tony JJuratowitch,
uratowitch, CChemical
hemical Plant
Plant OOwner
wnerr and
Paul
Plantt Owner
Paul HHarvey,
arvey, CChemical
hemical Plan
Owner
Eraring
Eraring PPower
ower SStation
tation
4:00
Condensate
silicaa lleakage
Conddensate polishing especially sodium
m and silic
eakage
Beryn
Beryn Adams,
Adams, Regional
Regional Technical
Technical Manager
Managger
Lanxess,
Singaporee
Lanxess, Singapor
4:25
Worsley
power
station
study::
Worrsley multi-fuel cco-generation
o-generation po
wer
e sta
tion ccase
ase study
polishing
heatt rrecovery
polisshing alumina refinery
refinery ccondensate
ondensate w
with hea
ecovery
for
for boiler
b
ffeed
eed
Leo
Leo KKearney,
earney, Commissioning
Commissioning EEngineer
ngineer
Veolia
Water
Veolia W
Waater SSolutions
olutions & Technolog
TTechnologies
echnologies
4:50
Questions
Questions
5:00
Close
Closse of Day
Day ttwo
wo
(Program
(P
rogram subjec
T u e s d a y 2 9 t h : E x p l o r e TTee r r i g a l
TTonight
onight is at
at your
your leis
leisure.Take
sure.TTake this opportunity
opportunity to
to wander
wander along
alonng TTerrigal
errigal beach loc
located
ated only
only a ststones
ones throw
thhrow from
from the hot
hotelel or
savour
sa
vour the local
local pr
produce
oduce and treat
treat yourself
yourself ttoo some of the local
local rrestaurants
estaurants and pubs
pubs..
CClick
lick her
ther information
information on restaurants
restaurants to
to visit in Terrigal.
Terrigal.
heree for fur
further
www
324
AP I PowerCh em
m 2012 Co
C n f eren ce, E xh i bi ti o n ann d Trai n i n g Co u rs es 3
PPCHEM
Events
Day 3 Wednesday 30th

SESSION
SE
SSION 7
8:45
Muja W
ater
Water
McNaugh
a ton, SSenior
enior Chemical
Chemical Analyst
Analyst
Kirk McNaughton,
Verve
Verve EEnergy
neergy
9:20
CCooling
ooling water
e management
onservation
water
management and resources
resources cconservation
aatt Loy
Loy YYang
ang B
Alicia
Alicia TTyler,
yler
yler, CChemical
hemical & Environment
Environment Officer
Officer
IMP Operations
Maintenance
tenance Pty
Operations & Main
Pty Ltd
Ltd
9:45
Minding yyour
ouur RRss and Qs
oving w
ater tr
eaatment
improving
water
treatment
Qs - impr
plantt performance
plan
performanc
ormance
Judy
Judy Weir,
Weirr, Powerplant
Powerplant Chemistry
Chemistry CConsultant
onsultant
Thermal
Thermal Chemistry
Chemistry Limited,
Limited, NNew
ew Zealand
Zealand
10:10
QQuestions
uestions
area
10:20
Morning TTea
eaa - Exhibition
Exhibition ar
ea
SESSION
SE
SSION 8
water
monitoring
10:45
Real time w
ater monit
oring at
at EEraring
raring Power
Power SStation
Station
Peter
Peter George,
George, CChemical
hemical PProjects
rojects Engineer
Engineer
Eraring
Eraring PPower
ower SStation
tation
11:10
Fairfield
water
Fairfield recycled
recycled water
water plant:
plant: A ccase
ase study in w
ater rrecycling
ecycling
Mark Nunn,
Nunnn, BBusiness
usiness Developer
Developer
Veolia
Water
Veolia W
ater Solutions
Solutions & TTechnologies
Technolog
echnologies
11:35
Stanwell
operational
elevated
Stanwell Power
Power Stations
Stations oper
ational response
response to
to ele
vated
salinity
river
salinity levels
levels in the FFitzroy
itzroy riv
er
Katrina
Katrina Hartnett,
Har
a tnett, GGraduate
raduate Chemist
Chemist
Stanwell
Stanwell Corporation
Corporation
12:00
Your
emissions
moree
Your cooling
coolingg water
water system
system affects
affffec
ects carbon
carbon emiss
sions mor
than you
think
world
you thi
nk - some real
real w
orld eexamples
xamples
Kevin
Kevin GGehan,
ehhan, Principal
Principal Consultant
Consultant
Nalco
Nalco Australia
Ausstralia
12:25
Questions
Questions
12:35
LLunch:
uncch: SSeasalt
easalt RRestaurant
estaurant
SESSION
SESSION 9
impactt of biof
biofouling
efficiencyy
1:30
TThe
he impac
ouling on the hhydraulics
ydrauulics and efficienc
off ccooling
o li pumping
ooling
i ccapacity
apacitity
LLudwin
udwin DDaal,
aal, Consultant
Consultant
KEMA,
KEM
A, The
The Netherlands
Netherlands
dissolved
from
ash
water
1:55
TThe
he rremoval
emoval of dissolv
ed metals fr
om as
sh dam w
ater uusing
sing
process
Station
the Metclean
Metclean pr
ocess - pilot trial aatt TTarong
arrong PPower
ower Sta
tion
BBradley
radley GGauci,
auci, PProcess
rocess EEngineer
ngineer
VVeolia
eolia Water
W
Waater Solutions
Solutions & Technologies
Technolog
Technologies
Removal
trace
elements
2:20
Rem
moval of selenium and tr
ace elemen
t with iriron
ts
on
through
adsorption/coo ooxyhydroxides
xyhhydroxides and iron
iron ooxides
xides thr
ough adsorption/c
precipitation
pr
eccipitation mechanism
Suzanne LLaucht,
aucht, EEnvironment
nvironment Manager
DDelta
elta EElectricity
lectricity
CapWa
water
membranes
2:45
CapW
Wa capture
capture of evaporated
evaporated w
ater bbyy membr
anes
LLudwin
udwin DDaal,
aal, Consultant
Consultant
KEMA,
KEM
A, The
The Netherlands
Netherlands
3:10
QQuestions
uestions
3:20
area
AAfternoon
fternoon
e
ttea
ea - EExhibition
xhibition ar
ea
3 45
3:45
discussion
(water)
PPanel
aneell disc
di ussion
i 2 (w
( ater))
4:15
Closing
Mikee Griffin
Clos
sing rremarks,
emarks, Mik
4:25
CConference
onfference closes
(Program
(P
Program subjec
TTee c h n i c a l TToo u r : T h u r s d a y 3 1 s t M a y
VVisit
isit AAustralias
ustralias lar
largest
geest gener
generating
ating ccapacity
apacity po
power
wer station
station - EEraring
raring Power
Power station
station rrecently
ecently upgraded
upgraded frfrom
f om 4 x 660M
660MW
W units to
to
720MW units wit
ange of auxiliar
efurbishmennts. Plan
our will include new Wet
Wet rracks
ackss and on-line monit
oring
4 x 720MW
withh a rrange
auxiliaryy plan
plantt rrefurbishments.
Plantt ttour
monitoring
instrumentation,
sewage
effluentt as a substitut
substitutee for domesticc w
water
instrumentation, Water
Water
e Treatment
Treatment Plant
Plant recovering
recovering trtreated
eated sew
wage effluen
ater used in industrial
industrial
processes,
system
pr
ocesses, and CW syst
em design
design features
feaatures and modifications.
modifications.
Eraring
located
Erarring Power
Power Station
Station is loc
ated approximately
approximatele y an hour from
from TTerrigal.
errigal.
TThursday
hursday 31st (9:
(9:30
:30 am - 4:30 pm) & FFriday
ridaay 1st (9:00 am - 12:30 pm
pm)
m) - Training
Training Courses
Courses
T1
Chemically influenced
influenced damage mechanisms
mechanisms in fossil
fossil and ccombined
ombined ccycle
ycle plan
ts
Chemically
plants
Barry Dooley,
Dooleyy, Senior
Senior Associa
te, Structural
Structural Integrity
Integgrity Associates,
Associates, Inc.
Inc. USA
Barry
Associate,
T2
Startup shutdown
sshutdown and layup
layup - pr
oper pr
eseervation of equipmen
Startup
proper
preservation
equipmentt
Jim Ma
theews, Program
Program Manager - Boiler
Boiler & Turbine
Turbinee Steam
Steam Cycle
CCyycle Chemistry
Chemistry Program,
Program, EPRI, USA
U
Jim
Mathews,
T3
Ion exchange
exchaange and membrane
membrane ttechnologies
echnologies ffor
or TDS rremoval
emoval
Ion
Wah-Hingg Siong,
Siong, Regional
Regional Technical
Technical Manager,
Managerr,, GE W
ater & Process
Process Technologies,
Technologies, Malaysia
Malaysia
Wah-Hing
Water
w w w.
w . a p i . e d u.
u.au
AP I PowerCh em
m 2012 Co
C n f eren ce, E xh i bi ti o n ann d Trai n i n g Co
C o u r se s 4
325
PPCHEM
Events
General Information
VVenue
enue & AAccommodation
ccommodation
CCrowne
rowne Plaza TTerrigal
errigal
Pine Tree
Tree LLane,
ane, Terrigal
Terrigal
Pine
Tel:
Tel: 02 4384 9111
www.crownneplazaterrigal.com.au
www.crowneplazaterrigal.com.au
SStandard
tandard Room
Room + Breakfast
Breakfastt for 1
Standard
Standardd Room
Room + Breakfast
Breakfast for 2
$175.00
$200.00
YYour
ou
ourr cr
credit
edit card
card details will need to
to be provided
provided ttoo guar
guarantee
antee yyour
our book
booking.
ing.
YYou
ou will be responsible
respponsible for pa
ying yyour
our ac
count dir
ectly ttoo tthe
he hot
el on yyour
our depar
ture.
paying
account
directly
hotel
departure.
accommodation
days
arrival
date
booking.
CCancellation
ancellationn of yyour
our ac
commodation within 14 da
ys of yyour
our ar
rival da
te will incur the full ccost
ost of yyour
ouur accommodation
accommodation book
ing.
TTransport
ransport
BByy Car
Crowne Plaza TTerrigal
Crowne
errigal is situated
situated just 90 minutes
minutes drive
drive frfrom
om SSydney.
ydney. PParking
arrking is aavailable
vailable onsite
onsite at
at the hotel
hotel for a flat
flat rrate
ate of $18 per day.
day.
AAlternatively,
lternatively, yyou
ou ccan
an use the CCouncil
ouncil ccar
ar park in W
ilson SStreet
treet ((directly
directly behind the hot
el) aatt no ccost.
ost.
Wilson
hotel)
BByy TTrain
rain
TTrain
raain fr
from
om SSydney
ydney (N
(Newcastle
ewcastle & CCentral
entral Coast
Coast line
line))
If yyou
ou don
dontt w
want
ant ttoo dr
drive
ive wh
whyy not ccatch
atch the trtrain
ain ttoo the cconference.
onference. TThis
his is appr
approximately
oximately 1 hour and 45min trtrip
ipp to
to GGosford
osford train
train station
station and from
from there
there a 20 minut
minutee (11k
(11km)
m) ccab
ab
rride
ide ttoo TTerrigal.
errigal. Please go ttoo w
www.cityrail.info
ww.cityrail.info for trtrain
ain timetables
timetables..
Airportt TTransfers
Airpor
ransffers
TTransport
ransport will be pr
provided
ovided for ddelegates
delegates as follo
follows:
ws:
SSunday
unday 27 M
May
ay : SSydney
ydney ttoo TTerrigal
errigal
3.30 pm
4.00 pm
p
4.30 pm
5.30 pm
depart
airport
depart SSydney
ydney air
poort ((domestic
domestic tterminal)
erminal)
p upp from
from Central
Central
a RRailway
ailway SStation
tation
pick
from Hornsby
Hornsby RRailway
ailway SStation
tation
pick up from
arrive Ter
Terrigal
arrive
Terrigal
W
ednesday, 30 M
ay : Terrigal
Terrigal ttoo Sydney
Sydney
Wednesday,
May
5.15 pm DDepart
epart CCrowne
rowne Plaza TTerrigal
errigal for SSydney
ydney air
port ((domestic
d
domestic
tterminal)...
erminal)...
airport
dr
dropping
opping off aatt HHornsby
ornssby Railway
Railway Station
Station and Central
Central Railway
Railway Station
Station if required.
required.
7.15 pm AArrive
rrive SSydney
ydney
d air
port domestic tterminal
erminal
airport
(subjec
(subjectt to
to traffic
traffic congestion)
conngestion)
TThursday,
hursday, 31 May
May and Friday
Friday 1 June : TTerrigal
errigal ttoo Sydney
Sydnney
departing
oncee each da
dayy ttoo SSydney
airport,
dropping
TTransport
ransport will be provided
provided
v depar
ting onc
ydney ddomestic air
port, dr
opping
departure
off aatt HHornsby
ornsby RRailway
ailway SStation
tation and CCentral
entral RRailway
ailway SStation
tation if rrequired.
eqquired. TThe
he depar
ture
arranged
majority
delegates
times will be ar
rangedd ttoo suit the major
ity of delega
tes rrequiring
equiring ttransport.
ransport.
Sunday 27th M
Sunday
May
ay : Golf
Shelly
Club,
Shelly
h ll BBeach
eachh Golf
G lf Cl
Club
b, SShelly
h ll BBeach
helly
eachh
If yyou
ou ar
aree in
interested
terested
e in playing
playing golf please rregister
egister yyour
our interest
interest on the registration
registration form.
form.
TTee
ee off will be frfrom
om
m 1:00pm. Costs
Costs and fur
further
ther infor
information
mation will be send to
to yyou
ou once
once yyou
ou
ha
ve registered
reegistereed your
your interest.
interest.
have
YYour
our Registr
our
Registration...
Registratio
ation...
1: Regist
Register
er on line aatt www.tmm.com.au
www.tm
mm.com.au
2: CComplete
omplete the aattached
ttached fform
orm
m and email ttoo meetings@tmm.c
meetings@tmm.com.au
om.aau
OR Fax
Fax 02 9810 7320
www
326
CConditions
onditions and CCancellations:
ancellations:
If yyou
ou ar
aree unable ttoo attend,
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substitutee delegate
delegate is welcome
welcome at
at no extra
extra charge.
charge. Where
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substitut
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vailable, a fee
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ted frfrom
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