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PPChem
PPChem 1 0 1
LESSON 12
Minimum-Level Instrumentation for Plant Cycle Chemistry
Monitoring
INTRODUCTION
Seven lessons of this series have dealt with feedwater and
boiler water treatments (Lessons 4 through 10). It has been
explained which chemical measures are required for the
optimum protection of materials in the feedwater train (the
part of the cycle between the condenser and the steam
generator) and for minimizing dissolution of the boiler tube
material and the protective layer formed on the water and
water/steam-touched boiler tube surfaces.
Advice with respect to the necessary extent of surveillance
of the feedwater and boiler water treatments will be given
in this lesson. Considering the staff shortages in the vast
majority of utilities and in particular at industrial steam and
power generators, the focus is on continuous monitoring
of cycle chemistry, although some information about pos-
sible additional surveillance via grab sample analyses will
also be given.
The configurations of utility plant cycles do not markedly
differ from each other. However, there are major differ-
ences in the configurations in industrial cycles, which are
often an integral part of the process or of systems for the
recovery of heat and energy. For this reason, only general
advice can be given as to the minimum level of instrumen-
tation. In the open literature, the terms "core parameters,"
"key parameters," and other similar designations are often
used for specification of the cycle chemistry-related instru-
ments essential for reliable cycle chemistry control (see,
e.g., Additional Reading).
It is very important that the instrumentation defined here as
the minimum level of instrumentation can be directly moni-
tored by the unit operator: displays and alarms in the con-
trol room may help staff to react promptly to any chemistry
upsets (values outside of a specified target range).
122
PPChem 101 – Fossil Cycle Chemistry /Imprint
FOSSIL CYCLE CHEMISTRY
MAKEUP TREATMENT SYSTEM EFFLUENT
(MAKEUP WATER)
The quality of the makeup is of great importance, in par-
ticular for cycles with once-through boilers and high-
pressure circulation (drum-type) boilers. The makeup has
to be demineralized. The lower the operation pressure, the
more relaxed the requirements on the makeup quality.
Industrial cycles with low operating pressure often receive
makeup consisting of partly demineralized water (e.g., by
way of reverse osmosis, electrodialysis, or softening).
Minimum-Level Instrumentation
Specific conductivity1 Monitoring of specific conductivity
is a very reliable monitoring tech-
nique. The specific conductivity
of chemically pure water is
0.055 µS · cm–1 at 25 °C (77 °F).
Any ionic contaminants present in
water increase its specific con-
ductivity.
Since all ionic contaminants con-
tribute to a conductivity increase,
this measurement is not specific.
Specific conductivity is tempera-
ture dependent. For this reason,
high-quality instruments with ex-
act temperature compensation
are required or the sample tem-
perature has to be adjusted to ref-
erence temperature (25 °C or
77 °F).
1
Specific conductivity is sometimes – in particular in Europe –
called "direct conductivity."
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PPChem 101 – Fossil Cycle Chemistry PPChem

Additional Instrumentation CONDENSATE

Condensate samples are typically taken from the conden-
Silica In certain makeup water treatment
sate extraction pump discharge although a direct sampling
plants (depending on the configu-
from the condenser is also possible. The condenser is the
ration of the makeup water treat-
most decisive cycle point with respect to the quality of the
ment system and the quality of raw
operating medium: contamination with cooling water via
water), monitoring of the silica con-
condenser leakage, ingress of regeneration chemicals with
centration in the makeup may be
treated makeup, and any impurities transferred from the
advantageous. In such cases,
condensate storage have to be detected before the actual
online silica monitoring is prefer-
feedwater train.
able to grab sample analyses (less
labor intensive).
In cogeneration units or in industrial units receiving return
Total Organic Carbon2 In certain cases, additional moni- condensate from the process, the condensate may be
toring of the total organic carbon contaminated by different contaminants. Additional moni-
may be advisable. This could be toring requirements may depend on the type of the indus-
the case when the raw water is trial process.
heavily loaded with organic matter.

Minimum-Level Instrumentation in Cycles with Once-

through Boilers and High-Pressure Circulation Boilers
MAKEUP OR CONDENSATE STORAGE
Cation conductivity Cation conductivity gives informa-
Makeup water or condensate stored in a tank may be sub-
tion about the presence and mag-
ject to contamination. The most typical contaminant is car-
nitude of contaminants introduced
bon dioxide originating from air. The condensate typically
by condenser leakage or from a
contains some alkalizing agent (ammonia or amines), and
makeup treatment system (e.g.,
the presence of other contaminants (originating from cool-
regenerant chemicals).
ing water ingress) cannot be excluded. For this reason,
monitoring specific conductivity as a quality criterion will Sodium Sodium ion acts as an indicator of
not be helpful. cooling water ingress in units with
seawater cooling or with other
cooling waters with a high content
Minimum-Level Instrumentation of dissolved solids. It is particularly
important for all units without con-
Cation conductivity3 When monitoring cation conduc-
densate polishers.
tivity, all cations present in the
sample are removed in a cation Oxygen Oxygen concentration in the con-
exchange column upstream of the densate is an indication of air-
actual conductivity sensor. The inleakage into the cycle.
sample downstream of the column
contains acids, formed via ion
exchange from ionic contaminants Minimum-Level Instrumentation in All Other Cycles
present in the original sample.
Increased cation conductivity indi- Cation conductivity Cation conductivity gives informa-
cates either ionic contamination or tion about the presence and mag-
contamination by air or both. Like nitude of contaminants introduced
the specific conductivity measure- by condenser leakage or from a
ment, monitoring cation conductiv- makeup treatment system.
ity is a non-specific measuring
technique.
For the abovementioned columns,
it is standard to use regenerated
strong acid cation exchangers that
change their color with exhaustion.

2 3
Note the difference between the total organic carbon (TOC) Cation conductivity is sometimes – in particular in Europe –
and dissolved organic carbon (DOC). called "acid conductivity" or "conductivity after cation
exchanger" (strong acid cation exchanger).

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PPChem PPChem 101 – Fossil Cycle Chemistry

CONDENSATE POLISHER EFFLUENT DEAERATOR OUTLET

Evaluation of the effectiveness of condensate polishers Oxygen monitoring at the deaerator outlet is not a neces-
and determination of the point of exhaustion (regeneration sary part of the minimum level of instrumentation.
demand) are the main goals of condensate polisher efflu- However, some operators use oxygen monitoring to check
ent monitoring. the efficiency of the deaerator.

Minimum-Level Instrumentation in Cycles with Once-

through Boilers and High-Pressure Circulation Boilers
Cation conductivity Cation conductivity readings in-
form the operator about the per-
formance of the polishers.
Sodium Sodium monitoring helps to recog-
nize any malfunction of a polisher
which is not detectable by the
cation conductivity measurement
(sodium removed from the sample
in the cation exchange column).
Minimum-Level Instrumentation in Industrial Cycles
The specification of the minimum level of instrumentation
in cycles with condensate return from industrial processes
depends on the type of possible contamination. In addition
to the instrumentation quoted under Minimum-Level
Instrumentation in Cycles with Once-through Boilers and
High-Pressure Circulation Boilers (cation conductivity and
sodium monitoring), monitoring of total or dissolved
organic matter or other techniques related to the detection
of the most probable contaminants may be required.
DEAERATOR INLET
In cycles with mixed metallurgy, minimization of copper
transport is vital. For this reason, the verification of reduc-
ing conditions in the condensate is very important.
FEEDWATER AT ECONOMIZER INLET
The major task of all monitoring instrumentation at the
economizer inlet is the evaluation of the total contaminant
ingress to the boiler. Since feedwater is typically used as
attemperation water for temperature control of the super-
heated or reheated steam, a possible ingress of contami-
nants to the steam is also determined.
Minimum-Level Instrumentation
Specific conductivity Specific conductivity supplies in-
formation about the ammonia level
in the feedwater and hence pH
during normal operation, since
other ionic impurity levels are
nearly negligible. In contaminant-
free cycles, specific conductivity
may be used as an indirect pH
measurement.
Cation conductivity Cation conductivity reliably detects
contamination by acidic or neutral
contaminants. However, contami-
nation by alkaline reacting contami-
nants is only imperfectly detected.
Oxygen Oxygen level is – in addition to the
pH – the most important and deci-
sive control parameter for all feed-
water treatments, including oxy-
genated, all-volatile oxidizing and
all-volatile reducing treatment.

Minimum-Level Instrumentation in Cycles with Mixed

Metallurgy
Oxidizing-Reducing The measurement of the ORP sup-
Potential (ORP) plies the necessary feedback for
establishment of a correct feed
rate of the reducing agent (prefera-
bly hydrazine).
Additional Instrumentation
BOILER WATER
Monitoring circulation (drum-type) boiler water chemistry
helps to establish conditions at which deposition and cor-
rosion in the boiler tubes is minimized. In addition, it allows
control of boiler water chemistry via blowdown and, in
units operated on phosphate or caustic treatment, control
of chemical feed. Furthermore, the saturated steam quality
depends among other things on the boiler water concen-
tration.

Reducing agent Additional monitoring of the con-
centration of the reducing agent at
the deaerator inlet may supply fur-
ther information for fine-tuning of
the reducing agent dosing.
For boiler water analysis, boiler drum samples or samples
from boiler downcomer(s) are typically used. Note that the
samples from the downcomer are diluted with the feedwa-
ter. For this reason, the levels monitored are lower in com-
parison to those from boiler drum samples.

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PPChem 101 – Fossil Cycle Chemistry
There are distinct differences in the minimum level of
instrumentation for boilers operated on different boiler
water treatments. For this reason, the minimum level of
instrumentation adequate for boiler water monitoring will
be given separately for each particular boiler water treat-
ment.
Minimum-Level Instrumentation – Boilers Operated on
All-Volatile Treatment (Oxidizing and Reducing)
Cation conductivity Cation conductivity monitoring is
the best indication of the level of
contamination entering the boiler
and of the concentration of con-
taminants resulting from circulation
in the boiler system.
Based on the cation conductivity
readings, the operator may estab-
lish the appropriate blowdown
rate.
pH The monitoring of the pH of the
boiler water is very important since
operation at too low of a pH could
result in serious corrosion attack
on waterwall tubes, in particular in
the presence of deposits. Note that
the actual local pH may be even
lower than the pH of the bulk boiler
water.
Additional Instrumentation
Specific conductivity Specific conductivity measure-
ment provides some information
when deviations from the normal
operation of the boiler occur. Addi-
tionally, specific conductivity read-
ings help in detecting malfunctions
of ammonia dosing in the conden-
sate or feedwater train.
Minimum-Level Instrumentation – Circulation Boilers
Operated on Oxygenated Treatment
Cation conductivity Cation conductivity monitoring is
the best indication of the level of
contamination entering the boiler
and of the concentration of con-
taminants resulting from circulation
in the boiler system. Based on the
cation conductivity readings, the
operator may establish the appro-
priate blowdown rate.
PowerPlant Chemistry 2009, 11(2)
PPChem
Oxygen The oxygen level in the boiler water
has to be controlled very strictly
since higher oxygen concentra-
tions and the presence of contami-
nants, in particular of chlorides, will
result in hydrogen-damage boiler
tube failures.
pH The monitoring of the pH of the
boiler water is very important since
operation at too low of a pH could
result in serious corrosion attack
on waterwall tubes, particularly in
the presence of deposits. Note that
the actual local pH may be even
lower than the pH of the bulk boiler
water.
Minimum-Level Instrumentation – Circulation Boilers
Operated on Phosphate Treatment
Specific conductivity Specific conductivity represents a
simple and reliable indication of
boiler water purity. In combination
with cation conductivity, it provides
an important tool for controlling the
actual concentration level of con-
taminants in the boiler water, and
in this way for establishing the
appropriate blowdown rate.
Cation conductivity In the presence of phosphate,
cation conductivity readings also
include the contribution of the
phosphate. This has to be consid-
ered when the level of contamina-
tion entering the boiler and the
contaminant concentration result-
ing from circulation in the boiler
system are evaluated.
pH The pH measured is influenced by
ammonia present in the boiler
water. This especially has to be
considered when the boiler is
operated with low phosphate con-
tent.
The monitoring of the pH of the
boiler water is very important since
operation at too low of a pH could
result in serious corrosion attack
on waterwall tubes, particularly in
the presence of deposits. Note that
the actual local pH may be even
lower than the pH of the bulk boiler
water.
125
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PPChem
Phosphate The determination of the sodium-
to-phosphate ratio is important for
mitigating excessive deposit build-
up and acid phosphate corrosion
underneath deposits.
Sodium The determination of the sodium-
to-phosphate ratio is important for
mitigating excessive deposit build-
up and acid phosphate corrosion
underneath deposits.
Sodium content readings help the
operator to establish the appropri-
ate blowdown rate and in this way
to attain a suitable saturated steam
quality.
Minimum-Level Instrumentation – Circulation Boilers
Operated on Caustic Treatment
Specific conductivity Specific conductivity represents a
simple and reliable indication of
boiler water purity. In combination
with cation conductivity, it provides
an important tool for controlling the
actual level of concentration of
contaminants in the boiler water
and in this way for establishing the
appropriate blowdown rate. It also
provides a direct indication of the
sodium hydroxide concentration
and is used to adjust the blow-
down rate and sodium hydroxide
dosing.
Cation conductivity This simple and reliable tool sup-
plies important information about
the concentration of contaminants
in the boiler water. In combination
with specific conductivity, it is used
to establish the appropriate blow-
down rate.
pH The pH measured is influenced by
ammonia present in the boiler
water. The monitoring of the pH of
the boiler water is very important
since operation at too low of a pH
could result in serious corrosion
attack on waterwall tubes, espe-
cially in the presence of deposits.
Note that the actual local pH may
be even lower than the pH of the
bulk boiler water.
126
PPChem 101 – Fossil Cycle Chemistry /Imprint
Additional Instrumentation – Circulation Boilers
Operated on Caustic Treatment
Sodium The determination of the sodium
content is import for two reasons:
a certain amount of sodium hy-
droxide is necessary for setting up
the required pH, and the sodium
content has to be kept under a cer-
tain level to ensure a suitable satu-
rated steam quality.
Additional Instrumentation Applicable to All Circula-
tion Boilers
Silica as a boiler water contaminant has a relatively high
volatility even at low operation pressures. In tight cycles
(no condenser leaks) with demineralized makeup contain-
ing ≤ 10 µg · kg–1 silica, the concentration of silica in the
boiler water is not a problem. However, in cycles in which
makeup water silica content is higher, with silica-contain-
ing cooling water ingress or when colloidal silica remains in
the treated makeup, increased silica concentration in the
boiler water may create problems with the formation of sil-
ica or silica-containing deposits in the low pressure tur-
bine.
Silica Silica monitoring is used to estab-
lish the appropriate blowdown rate
in cycles affected by high silica
content in the condensate or feed-
water and – after concentration in
the boiler circulation system – in
the boiler water.
SUPERHEATED OR REHEATED STEAM
The quality of the produced steam is very important, in
particular in cycles with condensing turbines. The quality
requirements may be a bit more relaxed if the steam-
receiving turbine is a backpressure turbine.
In cycles with circulation (drum-type) boilers, elevated
cation conductivity readings may be caused by increased
carryover. In all cycles, decomposition of organic matter
resulting in the formation of carbon dioxide or low molecu-
lar weight organic acid may be the reason for a cation con-
ductivity increase.
Units subject to peaking or cycling operation experience
higher cation conductivities due to the presence of carbon
dioxide (originating from air) in the steam.
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PPChem 101 – Fossil Cycle Chemistry /Imprint PPChem

Minimum-Level Instrumentation – Superheated or Particle Monitoring

Reheated Steam Particle monitoring is a relatively new monitoring tech-
nique. It allows the detection of very low levels of particu-
Cation conductivity Continuous measurement of cation
late metal oxides (< 2 µg · kg–1) in plant cycle streams and
conductivity provides a reliable
the automatic obtaining of a sample for laboratory analysis
indication of the presence of steam
when the reading exceeds a preset threshold. This moni-
contaminants. Some of these are
toring technique may help in operating and maintaining the
known to cause turbine corrosion.
reliability of steam generation systems.
Sodium Since during the cation conductiv-
ity measurement all cations are Read the following contribution for more information:
removed in the cation exchange Breckenridge, R. A., Hancock, L. J., Bryant, R. L., Clark, J.
column, excessive contamination W., PowerPlant Chemistry 2006, 8(10), 609–615.
of steam by sodium hydroxide
cannot be identified by way of
cation conductivity monitoring.
CLOSING COMMENT
The huge variety of cycle designs, in particular in com-
bined cycles with heat recovery steam generators and in
OTHER CONTINUOUS CYCLE CHEMISTRY
installations for heat or energy recovery in the process
MONITORING TECHNIQUES
industry, make it basically impossible to give a compre-
Three further monitoring techniques may help in some criti- hensive overview of the minimum level of instrumentation
cal cases in upgrading information about the actual chem- for plant cycle chemistry monitoring that considers the
istry conditions within the plant cycles: details of all designs. Nevertheless, it is hoped that the
information presented will help not only operators of utility
– degassed cation conductivity
units but also all engineers and chemists responsible for
– ion chromatography cycle chemistry in combined and atypical industrial cycles.
– particle monitoring
The monitoring aspects related to cycles operated on
some of the possible "all-organic" chemistries are inten-
tionally not dealt with. The assumption is that the minimum
Degassed Cation Conductivity level of instrumentation will not differ from that in compara-
ble units operated on "classic" cycle treatments. In case of
Degassing of the cation conductivity sample removes car-
doubt, the supplier of the organic additives must be con-
bon dioxide from the sample. All other acidic contaminants
sulted.
(originally present in the sample upstream of the cation
exchange column as salts of inorganic or organic acids)
remain in the sample. The application of degassed cation
conductivity monitors may, for example, help to reduce
costly holds during startup when the increased cation con- REMARK
ductivity is caused by carbon dioxide.
The International Association for the Properties of Water
and Steam is preparing a Technical Guidance Document
Read the following contribution for more information:
dealing with instrumentation for monitoring and control of
Rziha, M., Wuhrmann, P., PowerPlant Chemistry 2007,
cycle chemistry for the steam/water circuits of fossil-fired
9(11), 644–648.
and combined cycle power plants. This document is
expected to be approved in autumn 2009. Check out the
IAPWS homepage at http://www.iapws.org/ in October
Ion Chromatography 2009.
Modern ion chromatographs can be set up for online op-
eration. Continuous ion chromatography may be used to
monitor corrosive ions at very low detection limits (very
often at sub-µg · kg–1 (sub-ppb) levels) in plant cycle
streams and in this way to indicate any contaminant
ingress.

Read the following contribution for more information:

Newton, J. B., Jensen, D., PowerPlant Chemistry 2006,
8(11), 652–657.

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PPChem PPChem 101 – Fossil Cycle Chemistry /Imprint

ADDITIONAL READING Imprint

All those interested in plant cycle chemistry monitoring
Editor: Albert Bursik
may find additional information in the following cycle
Publisher: PowerPlant Chemistry GmbH
chemistry guidelines:
P.O. Box 1269
68806 Neulussheim
Cycle Chemistry Guidelines for Fossil Plants: All-Volatile Germany
Treatment, Revision 1, 2002. Electric Power Research Phone: +49-6205-392273
Institute, Palo Alto, U.S.A., 1004187.
Fax: +49-6205-37883
Cycle Chemistry Guidelines for Fossil Plants: Phosphate E-mail: info@ppchem.net
Continuum and Caustic Treatment, 2004. Electric Power editor@ppchem.net
Research Institute, Palo Alto, U.S.A., 1004188. Homepage: http://www.ppchem.net
Cycle Chemistry Guidelines for Fossil Plants: Oxygenated International Advisory Board:
Treatment, 2005. Electric Power Research Institute, Palo R. B. Dooley (Structural Integrity Associates, USA)
Alto, U.S.A., 1004925. M. Gruszkiewicz (ORNL, USA)
Professor Klaus R. G. Hein (Stuttgart University, Germany)
Guidelines for Feed Water, Boiler Water and Steam Quality Professor D. D. Macdonald (Pennsylvania State University,
for Power Plants/Industrial Plants, 2004. VGB PowerTech, USA)
Essen, Germany, VGB-R 450 Le. M. Sadler (United Kingdom)
H.-G. Seipp (Germany)
U. Staudt (VGB PowerTech, Germany)
R. Svoboda (ALSTOM (Switzerland) AG, Switzerland)
Editing and copy reading: Kirsten Brock

IN CLOSING Technical Illustrations and Desktop Publishing:

This lesson, like all others in this series, is intended to help
all non-chemists responsible for chemistry-related tasks,
all power industry newcomers, and all engineers, whether
chemists or non-chemists, to learn the fossil cycle chem-
istry basics. It is a great challenge for us to support you in
your efforts to improve the plant cycle chemistry in your
plants.
With this lesson, PPChem 101 – Fossil Cycle Chemistry is
completed. PowerPlant Chemistry acknowledges the
mostly very positive response from its readers. Your
recommendations with respect to comparable future
projects are appreciated.
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