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Chloride Contamination of the Water/Steam Cycle in Power Plants Part I:

Evidence from a Case Which Could Not Be Explained in Terms of Currently
Familiar Sources

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 PPCHEM Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I

Chloride Contamination of the Water/Steam Cycle in Power Plants

Part I: Evidence from a Case Which Could Not Be Explained in
Terms of Currently Familiar Sources

Emmanuel K. Quagraine and Jonathan P. Ruffini

ABSTRACT
This is the first of a three-part publication series on the findings from investigations performed at the Shand Power
Station of SaskPower to determine a hitherto unfamiliar source(s) of chloride contamination to the water/steam circuit.
For this plant, which is usually on automatic grid control (AGC), unit ramping is common and there is some reason to
associate this with the initiation of the chloride ingress. The present paper presents a systematic approach to examin-
ing the various familiar sources currently known to plant operators, chemists and the like as potential culprits and pro-
vides the bases for eliminating these as responsible agents in this case. Based on routine plant operating data and
purposeful intermittent grab sample analyses as well as numerical analysis of chloride cycling in the boiler, these well-
known potential causative factors, which include condenser tube water leaks, make-up chloride, halo-organics from
the water treatment plant, and contaminated ammonia feed sources, could not be found to individually or cumulatively
account for the magnitude of chloride contamination observed in this plant. The extent of the chloride cycling required
too frequent blowdowns from the boiler, and a cost analysis of the implications from such frequent blowdowns is also
Author's Copy

presented as one of the incentives that drove the search for the root cause of such a level of contamination. There
were some indications that surplus condensate from the hotwell to the boiler make-up storage tanks was a significant
chloride origin, but this could not account for the level of contamination, and the source seems to be distinctly differ-
ent from the traditionally known condenser tube water leaks. Furthermore, there were some indications that ammonia
injection was associated with the chloride crises, although there was ample evidence to eliminate this as the source.
These associations formed the basis for further investigations, the findings of which will be reported as Part II and Part
III of this series.

INTRODUCTION
Chloride is a well-known corrosive inorganic ion, which
can potentially cause or contribute to equipment break-
down, e.g. boiler tube failures from acid chloride attacks
and steam turbine failures from chloride stress corrosion
of turbine blades [1–5]. It is specifically noted to contribute
to the following [6]:
(a) Corrosion fatigue, stress corrosion cracking (SCC),
and pitting in low-pressure (LP) turbines;
(b) Corrosion, hydrogen damage, and pitting in boilers;
and
(c) Synergistic effects on drum boiler waterwall corrosion
in the presence of oxygen and copper oxide.
For instance, it has been reported that in oxygenated,
high-temperature water (T= 288 °C and a dissolved
oxygen (DO) content of 8 mg · kg–1), the addition of
10 µg · kg–1 to 50 µg · kg–1 chloride to low-alloy steel
reactor pressure vessels resulted in acceleration of stress
corrosion cracking (SCC) crack growth rates in all investi-
gated materials by at least one order of magnitude [3].
Even for steam turbine blade steels of sufficient alloy (e.g.
high Cr) content, which demonstrate resistance to pH (or
CO2)-induced corrosion, a higher chloride content in the
water resulted in higher corrosion rates [7]. Especially in
locations where water flow adjacent to the tubes is dis-
rupted and excessive deposits are bound to occur,
chloride is a typical example of an acidic boiler contami-
nant that may concentrate up to dangerous levels to
cause hydrogen damage [5].
There are various known sources of chloride ingress into
the water/steam cycle, which include the following: make-
up water contamination [6,8], feedwater contamination
from sources such as condenser tube leaks [6,9] and/or

© 2012 by Waesseri GmbH. All rights reserved.

98 PowerPlant Chemistry 2012, 14(2)

 Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I
leaks from condensate pump seal cooling water for the
condensate pumps [10], leakages from condensate
polishers [4,8], and via contaminated chemical injections
[9]. According to Bursik [11], heteroatom-containing
organics, of which trihalomethanes (THMs) are part, are
the most dangerous contaminants in make-up water for
utility and industrial plant cycles. About 90 % of THMs
have been noted to pass through water treatment plants
of a nuclear plant [8], and this has partially been impli-
cated in an "acid"-chloride boiler leak due the breakdown
of the organochlorides that escaped the make-up water
treatment plant [8]. THMs can also enter the water/steam
cycle through other routes. For example, the accidental
introduction of trichloroethane into the condensate of a
once-through boiler plant through an oxygen supply line
which had previously been degreased with 1,1,1-
trichloroethane (and not blown dry afterwards) was
reported [12]. The gradual decomposition of the contami-
nant at different places along the feedwater and steam
path was observed by the measurement of acid conduc-
tivity, which was due mainly to chloride.
Condenser leaks are a major source of contaminants in
the water/steam circuits and feeding of contaminated
Author's Copy
condensate to vulnerable components (such as attemper-
ator sprays, etc) can be detrimental [13]. For this reason,
condensate polishing units are recommended to avoid
such problems [10]. However, chloride leakages from con-
densate polishers are also known to occur [4].
This paper is the first of a three-part series reporting the
findings from investigations performed at the Shand
Power Station of SaskPower to identify the root cause of
chloride contamination of the water/steam cycle experi-
enced in the plant, which appeared quite illusive initially.
This current paper focuses on the systematic steps taken
by this plant to ascertain whether any of the commonly
known routes of chloride contamination were responsible
for the contamination. The objective of the paper is to
convince its audience that there are some situations
where the popularly known routes such as the traditional
condenser tube water leak, make-up contamination,
chemical contamination, etc (as tempting as they may be
as potential sources) cannot be logically justified. This
gives room to search for alternative sources or routes as
the actual root cause(s).
STATEMENT OF THE PROBLEM
With high sulphate to chloride ratios (typically ranging
between (6–7):1) in the re-circulating water at this station,
condenser leaks typically result in the same sulphate to
chloride ratio in the condensate and in the feedwater.
Likewise, any weepy condenser water leak into the hotwell
is expected to follow the same trend and hence the plant
would typically blow down from the boiler drum (with EPRI
PowerPlant Chemistry 2012, 14(2)
PPCHEM
guidelines) based on higher sulphate contamination and
not chloride. Higher sulphate to chloride ratios in the
water/steam cycle could sometimes also occur as a result
of sulphate ingress from the make-up treatment system.
Since January 2009, however, the basis for the blowdown
from the boiler drum at Shand Power Station has changed
from sulphate based to chloride based, as the ratio of
chloride to sulphate was consistently higher in the boiler
drum. Figure 1 shows the relation between unit load/LP
exhaust pressure with the boiler chloride concentration for
periods preceding when the chloride issues in the boiler
drum seem to have become serious or begun and imme-
diately thereafter. From the figure, it is tempting to point to
the preceding unit ramping as a significant contributor to
or initiator of the chloride ingress into the water/steam
cycle. Prior to this occurrence, the unit since the start-up
conditions on November 9, 2008 had operated without the
need for boiler blowdown due to water chemistry, and the
chloride (and sulphate) concentrations in the boiler drum
had remained essentially constant.
The impact of chloride ingress into the water/steam cycle
can potentially be very damaging as alluded to in the intro-
ductory section and could have a significant cost associa-
tion in terms of, for example, boiler tube and steam turbine
failures if not handled properly. Ignoring the impact of
chloride (and for that matter cycle chemistry) in keeping a
unit in operation is therefore totally irresponsible and not
an option; any unit operated under such conditions is
bound to spiral to complete destruction, with its conse-
quential billions of dollars in losses. Under conditions of
moderate ingress of impurities, however, boiler blowdown
is one of the recommended options to keep a unit in oper-
ation whilst making sure the cycle chemistry (e.g. chloride
levels in the boiler) is within acceptable limits that mini-
mize the risk of deposition and corrosion in the
water/steam cycles and thus protect both the boiler and
turbine [6]. There are, however, also some drawbacks
associated with boiler blowdowns, especially if they occur
too frequently.
Although the financial cost associated with efficiency
reduction (i.e. heat rate effect) from continuous blowdown
of the boiler (CBD), on its own and for a coal-fired power
plant unit such as this one, is only moderate, there are
other costs associated with CBD which are more signifi-
cant. For example, estimated fuel costs associated with
chloride-based CBD for the year 2010 and for January 1 to
April 10, 2011, when the chloride contamination was of
significant proportions, were only $5,826 and $2,078
respectively for this coal-fired unit (i.e. at a fuel cost of
$1.395 per GJ), which translates to about $14,993 and
$5,348 respectively for an equivalent natural gas-fired unit
(at a fuel cost of $3.590 per GJ). However, the frequent
CBD gave rise to more significant costs in terms of
increased frequent maintenance requirements to replace
the motor-operated blowdown valve, and the associated
99
 PPCHEM Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I

(a)
350 140

300 120

LP Exhaust Pressure [kPa x 10]

250 100

Concentration [µg · kg –1 ]
Unit Load [MW]

200 80

MW generated, left axis

150 Boiler SO4, right axis 60

LP exhaust, right axis
Boiler Cl, right axis
100 40

50 20

0 0
13-Nov 14-Nov 15-Nov 16-Nov 17-Nov 18-Nov 19-Nov 20-Nov 21-Nov 22-Nov 23-Nov 24-Nov
Date in 2008

(b)
Author's Copy

350 120

300
100

LP Exhaust Pressure [kPa x 10]

250

Concentration [µg · kg –1 ]
80
Unit Load [MW]

200

60
MW generated, left axis
150
Boiler SO4, right axis
LP exhaust, right axis 40
100 Boiler Cl, right axis

20
50

0 0
15-Jan 16-Jan 17-Jan 18-Jan 19-Jan 20-Jan 21-Jan 22-Jan 23-Jan 24-Jan
Date in 2009

Figure 1:
Unit load and low pressure (LP) exhaust pressure versus chloride and sulphate concentrations in the boiler drum
for periods preceding the chloride contamination (i.e. in November 2008) (top) and in the period when the issue
started (January 2009).

piping and headers. In addition, it created safety concerns
due to the wear down of this equipment and the potential
for unexpected and sudden steam leakages. To illustrate,
although the CBD motor-operated valve and the header
and connecting piping were replaced in 2005/2006, the
frequent chloride-based CBD led to their premature
replacement during the crises period (January 2009 to
April 2011), costing a total amount of $45,390 to date; an
additional cost of about $29,362 is also anticipated during
the major overhaul in 2012 to replace the header and
some sections of the connecting piping again. As this
maintenance work requires unit outages to complete,

100 PowerPlant Chemistry 2012, 14(2)

 Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I
there are huge cost implications from the viewpoint of loss
of generation. Based on a total duration of approximately
45 to 54 days recorded (and/or estimated) from the plant
SAP maintenance records to complete these jobs, as
much as approximately $18,400,000 to $22,100,000 in
lost generation is possible due to these repairs (using a
fuel compensated electricity cost of $55.90 per MWh).
As most of the repairs (in this case) were done during
scheduled maintenance outages, when other required
maintenance work was also completed, the estimated
loss of generation cost above would, arguably, not have to
be exclusively attributed to the frequent CBD-related
repairs. A counterargument would be that the associated
cost in lost generation could even be more than the esti-
mates above if these had to be done unplanned as a result
of forced outages, in which case other factors such as
parts delivery etc could play a significant role by extending
the duration of the outages. In any case, the above cost
analysis illustrates that there are huge financial implica-
tions, directly or indirectly, from using boiler blowdown as
a corrective action to address such water chemistry
excursions, especially under conditions where the ingress
of contaminants leads to too frequent blowdowns.
Author's Copy
Furthermore, it has to be realized that CBD is only a reac-
tive measure and does not address the root cause of the
chloride contamination. It was also not going to be sus-
tainable, especially as the chloride contamination contin-
ued to increase, and would subsequently have resulted in
an increasing frequency of blowdowns with time. With the
condenser earmarked to be replaced soon, it was tempt-
ing to falsely rely on that as a hopeful solution. However,
replacing the condenser without knowing the mechanism
or means by which chloride is selectively entering the
water/steam cycle (even if associated with the condenser)
may not be the right corrective action, as it does not
address the root cause if this is unknown and has not
been dealt with (properly) during the tube replacement
process. It was therefore crucial to identify the source of
this contamination and apply the necessary and more
effective corrective action.
Different sources of potential chloride contamination were
considered as suspects and were investigated: the aqua-
ammonia injection system for pH control in the
water/steam cycle, halo-organics from the boiler make-up
water, condenser water leakage and, lastly, direct chloride
contamination of the make-up storage tanks from the hot
condensate draining (HCD) system and/or the plant's
closed circuit cooling water (CCCW) for plant equipment
such as boiler feed pumps, soot-blowers, and pulverizers.
The CCCW and HCD systems are tied to the make-up
storage tanks and hence contamination was a real possi-
bility with valve failures in the former or inadvertent trans-
fer from the latter without prior knowledge of the water
quality.
PowerPlant Chemistry 2012, 14(2)
PPCHEM
Responses from consulting with colleagues through the
FOMIS platform indicated that the most common root
cause of chloride contamination in boiler drums is due to
condenser tube leaks, even if only small leaks occur [9].
Contaminated ammonia injected into feedwater for pH
control was also noted but as a less common possibility. It
was further noted that this latter potential source could be
eliminated by verifying that the supplier had made no
process changes and by testing samples. Some specific
experience shared included water/steam cycle chloride
contamination from a leak at the base of a condensate
pump that was introducing stagnant water. In a different
FOMIS report [14], high chlorides (occasionally up to
150 µg · kg–1) in the boiler drum with sodium levels only at
1.2 µg · kg–1 had been experienced and it was considered
that this was likely to be associated with high chloride
concentrations in the caustic regenerant used for the con-
densate polisher, which was being fouled with iron and
was suspected to be the source of the contaminant. A
membrane grade caustic was indicated to have a typical
chloride level of 100 mg · kg–1, whilst a diaphragm grade
caustic can have levels as high as 10 000 mg · kg–1 (i.e.
1 %) [14]. (The cause of the iron fouling of the resin had
also been determined by others to be due to high dis-
solved iron in the caustic regenerant.) EPRI's cycle chem-
istry guidelines document gives condenser leakage and
condensate polishers (but not ammonia feed systems) as
possible causes of chloride excursions and includes
make-up demineralizers as another source [6].
The following is a discussion of the step-by-step
approach used to evaluate the various potential sources
of water/steam cycle chloride contamination presented
above and the reasons why we believe they were not the
main culprits responsible for the contamination experi-
enced by this plant that led to increasingly frequent blow-
downs from the boiler to keep it in operation.
MATERIALS AND METHODS
Plant Design and Operating Conditions
Shand Power Station of SaskPower, a 305 MW coal (lig-
nite)-fired single unit power plant, has followed zero liquid
discharge (ZLD) requirements since commission in 1992.
Cooling Water System
Ever since the early stages of operation, the plant has
drawn mainly on a blend of secondary treated sewage
water (after passage through constructed wetlands) and
surface water as make-up water for re-circulating water in
the cooling tower (CT) although snow melts and rains
gathered in a yard drainage system contribute a small por-
tion. The proportions of the blend vary significantly
101
 PPCHEM Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I

throughout the year, but are close to 100 % surface water The Water/Steam Circuit
between November and April and variable fractions of sur-
A schematic of the condensate make-up system and the
face and secondary treated sewage during the months of
boiler water/steam system, which depicts a typical drum-
May to October. During this latter period, which is the lim-
type boiler, together with the condenser cooling re-circu-
ited operating period of the constructed wetland, an
lating water system at the Shand Power Station is shown
approximately equivalent total volume from each of the
in Figure 2. Some chemical treatment programs in these
two sources (~50 % each) is received at the station for
systems which are relevant to this discussion have also
mainly cooling. Two 50 % re-circulating water pumps sup-
been indicated as possible sources of chloride contamina-
ply water through a 2-pass, Cu-Ni (90:10 in the condens-
tion to the water/steam cycle. The designed condensate
ing zone and 70:30 in the air cooling zone) condenser at a
flow is 198 kg · s–1 and the normal boiler make-up is
designed total rate of 7 700 L · s–1 with a water velocity of
2.46 kg · s–1. The firing boiler water volume is 216 400 L.
2.4 m · s–1 through tubes and a ⌬T across the condenser
The chemical treatment program for the water/steam
of 12.3 °C for the maximum design heat rate of the plant.
cycle is all-volatile oxidizing (AVT(O)). Ammonia (28 %) is
The designed hot (inlet) water temperature to the cooling
added for pH control at a typical rate of 2 115 kg per year
tower (i.e. the outlet water temperature from the con-
or only 5.1 mL · min–1, but it is injected in diluted form (with
denser) is 42.3 °C. The average flow during the investiga-
demineralized water) into the water/steam cycle.
tion and used in the calculations in this paper was about
7 500 L · s–1.
Water/Steam Cycle Chemistry and Make-up Water
An induced draft counter flow cooling tower (open re-cir-
Quality Monitoring
culating system) is used for heat rejection. There are two
towers: a main tower of precast concrete construction Apart from typical on-line continuous monitoring of
with 7 cells, where water is sprayed and falls through parameters such as sodium, pH, conductivity (specific
ceramic fill, and an auxiliary tower of 2 cells made of a and/or cation), dissolved oxygen (DO), and silica at the
Author's Copy

fibre glass structure and polyvinyl chloride (PVC) fill. In applicable recommended sampling locations such as the
normal operation, all cells in the former are in service, boiler/steam drum, after the condensate extraction pump
whilst the two cells in the latter are used only when (CEP), and at the economizer inlet or the outlet of the last
required under high temperature and humidity conditions. high-pressure (HP) heater #6, daily grab samples and test-

Steam lost

Steam/condensate
return
Steam turbine

H2SO4 Circulating water

(cooling tower) Air
Cooling water Feedwater
ingress High pressure
Bleach Water heater #6
Condensate Steam
Condenser
extraction boiler
hotwell
pump
NH3
Make-up
Surplus

Hot NH3 NH3

condensate
drain tank Blowdown

Closed
Low level High level Ammonia
circuit
condensate condensate tank
cooling
tank tank
water

Water Demineralized
treatment storage
plant tank

Figure 2:
A schematic of the condensate make-up system and the boiler water/steam system together with the condenser cooling re-circulating
water system at the Shand Power Station.

102 PowerPlant Chemistry 2012, 14(2)

 Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I
ing are typically performed to ensure the integrity and reli-
ability of this on-line instrumentation and for the appropri-
ate remedial actions. For this power plant, the most critical
parameter for early detection of condenser leaks is
sodium at the CEP outlet, which other parameters are
used to confirm.
In keeping with EPRI's guidelines [6,15], apart from some
start-up conditions when silica is an issue, most of the
requirements to blow down from the boiler/steam drum
are based on sulphate or chloride. For these ions, the
facility has two Dionex-IC instruments: the IC-DX-2000 for
measuring these ions from grab sampling and the IC-DX-
800 as an on-line instrumentation. The latter is currently
programmed to gather the spectrum at 30 min intervals
from three sampling lines in the sequence: boiler drum,
high level (HL) tank and demineralized tank. Thus, each of
these samples is recorded approximately every half an
hour on a continuous basis. There is the capability to
include other sampling lines, but we typically focus on
these three. Although it should be possible to integrate
these readings into our on-line data-logging system, this
has not yet been done and hence the information is
accessed only from a localized computer attached to the
Author's Copy
IC. The IC-DX-2000 measurements on grab samples are
at the moment performed less frequently (i.e. about 1 to 2
times per week) with the sole aim of checking the accu-
racy and the reliability of the on-line measurements. In
instances when the IC-DX-800 is non-functional, more
regular measurements are taken, typically once a day. It is
also operated more frequently during start-ups and up-set
conditions.
RESULTS AND DISCUSSION
Make-up Sources
Chlorides from the Make-up Dosing Tanks For this
plant, there are at least 5 possible ways that the make-up
dosing tanks and subsequently the water/steam cycle
could be contaminated with chloride (see Figure 2):
(a) contaminated ammonia injection into the low level (LL)
and high level (HL) condensate tanks;
(b) slippages from the demineralizing beds in the water
treatment plant (WTP);
(c) contaminated water pumped from the hot condensate
drain (HCD) tank to the LL tank without prior water
quality checks;
(d) failure of isolating valves, to causing back feed from
the plant's closed circuit cooling water (CCCW) used
for cooling plant equipment (such as boiler feed
pumps, soot-blowers, and pulverizers); and
(e) surplus from the hotwell to the make-up feed tanks
(i.e. HL tanks).
PowerPlant Chemistry 2012, 14(2)
PPCHEM
The injected diluted ammonia, apart from delivering
directly to the pipeline after the condensate extraction
pumps, is also partly directed through the LL tanks and HL
tanks for eventual discharge into the hotwell (Figure 2).
Elimination of ammonia contamination as a major contrib-
utor to the chloride-based boiler blowdown is discussed
in a separate section (see below) and the explanations
given are applicable irrespective of the injection route.
Slippages from the demineralizing bed are possible, but
this is an easy source to eliminate or confirm as the quality
from the beds is monitored on a routine basis. The relative
amount of the various parameters would give a clue as to
whether this is a major source of the chloride ingress.
Furthermore, such slippages are quite intermittent and are
not usually persistent enough to account for the constant
chloride cycling in the boiler drum.
To eliminate the HCD tank as the source, this tank was
isolated from the LL tanks and the condensate water con-
tent put to waste. During the period that the tank was iso-
lated, no obvious improvement was observed with the
chloride cycling. The CCCW system is normally isolated
from the condensate tanks (LL and HL), but some previ-
ous experience had indicated the possibility of an isolation
valve failure that could allow the CCCW water, which was
of substantially poorer quality, to be back feeding into the
LL tank. At least on one occasion (January 13, 2011), the
CCCW was found to be of significantly higher chloride to
sulphate concentration ratio (11.9:1). To eliminate this
potential source (and in fact the HCD tank too at the same
time), the LL tanks were isolated from the HL tanks that
day (11:30 pm) so that the demineralized water was
directly delivered to the HL tank. The LL tank was kept
isolated for about 3 months, but no significant improve-
ment was seen with respect to the chloride cycling (see
Figure 3). As shown in the figure, the boiler blowdowns
before and during the LL tank isolation continued to be
based on chloride and were at a consistent frequency of
every 3 to 5 days. Furthermore, apart from some periods
during which a condenser leak occurred (i.e. February 21,
2011), the sulphate concentrations in the boiler drum were
typically significantly less than the chloride concentra-
tions.
Surplus from the hotwell to the make-up dosing tanks can
be tricky to both identify and eliminate as this is difficult to
monitor and control. However, such a source is only an
indirect source with its actual roots in the condenser,
either as a condenser water leak, which has been dis-
cussed as an unlikely major source of the experienced
chloride cycling, or as gaseous chlorine compound
ingress, which is discussed later in a separate paper.
Furthermore, such contamination of the make-up water
(HL) would only be intermittent (and not continuous) and
as the HL tank is more regularly monitored for chloride
(and sulphate), it would be noticed. For example, outside
the LL tank isolation period, some exceptionally higher
103
 PPCHEM Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I

350 4.0

3.5
300

MW generated, left axis 3.0

Condenser leak
Cl & SO4 Concentration [µg · kg –1 ]

250 Cl concentration, left axis

Blowdown Rate [kg · s –1]

SO4 concentration, left axis
2.5
Boiler CBD, right axis
Unit Load [MW]

200
Start of LL Carbon beds in parallel
2.0
tank isolation
150
1.5

100
1.0

50
0.5

0 0
1-Jan 8-Jan 15-Jan 22-Jan 29-Jan 5-Feb 12-Feb 19-Feb 26-Feb 5-Mar 12-Mar 19-Mar 26-Mar 2-Apr 9-Apr
Date in 2011

Figure 3:
Unit load versus chloride and sulphate concentrations in the boiler drum for periods preceding (January 1 to January 13,
Author's Copy

2011) and during (January 14 to April 8, 2011) the low level (LL) tank isolation.

chloride contents (11.7± 3.0 µg · kg–1) were observed in As all five listed sources end up in the HL tanks (and chlo-
the HL tank for December 3 and 4, 2010, as compared to ride levels are routinely measured from these tanks) before
the sulphate concentration (9.7±1.0 µg · kg–1) even though injection into the hotwell as make-up, a simple mathemat-
the demineralized tanks that fed the HL tanks contained ical calculation can also be performed to estimate the
only 2.5±1.2 µg · kg–1 chloride but higher sulphate contribution of these sources (as composite) to the boiler
(4.5±0.9 µg · kg–1). Such high chloride concentrations in drum cycling, provided the make-up rate is known.
the HL can significantly impact on the chloride cycling (i.e. According to this calculation (Method 1 of Appendix A), it
~11.5 µg · kg–1 Cl–1 increase per day in the boiler drum), could take about 28 days for the chloride ingress of
but the source is unlikely to be from the water treatment 4 µg · kg–1 (the highest recorded during the LL tank iso-
plant, leaving the HCD, CCCW, and hotwell surplus as lation) to result in boiler blowdown based on EPRI's
likely culprits. Since later investigations (see above) by guidelines of ~110 µg · kg–1 under the typical operating
isolating the LL tanks eliminated the HCD and CCCW as pressures in this plant for action level 1 response. It was
the dominant culprits for the persistent chloride cycling therefore concluded that potential contamination of the
(Figure 3), the hotwell surplus remained the most likely make-up water was not responsible for the frequent chlo-
source of the HL tank chloride contamination and subse- ride-based blowdown (for instance, once every 3–5 days
quently the water/steam cycle chloride contamination. In experienced at its peak).
support of the hotwell as the likely culprit is the intermit-
tent nature of the HL tank contamination. The average The conclusion above based on mathematical estimation
chloride concentration in the HL tanks the following day is further supported by grab sample measurements of the
(December 5, 2010) was only 4.3±1.1 µg · kg–1 whilst the water quality in the HL tanks as compared to that from
sulphate was higher at 17.3±3.9 µg · kg–1, indicating that post CEP and HP heater #6. With the low typical make-up
the source was probably the demineralized water (i.e. rate, MR = 2.46 kg · s–1, as compared to the condensate
1.0±0.1 µg · kg–1 Cl–1 and 8.5±2.8 µg · kg–1 SO42–) that fed return, R, of 198 kg · s–1, contaminant concentrations in
the HL tank. The intermittent significantly higher chloride the make-up (MX) cannot exceed the feedwater concen-
(than sulphate) levels also found in the HL tanks during the tration (FX) of this contaminant, which mathematically
chloride crises are therefore attributed to surplus conden- speaking is the make-up flow rate (MR) over the total
sate from the hotwell when it was contaminated with chlo- feedwater flow rate (FR) fraction of this concentration, i.e.
ride. The likely source of chloride contamination of the
MR
condensate water in the hotwell is discussed in detail in a FX = –––– · MX (1)
separate paper of this series. FR

104 PowerPlant Chemistry 2012, 14(2)

 Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I
Within the period of the LL tank isolation from the HL tanks
(Figure 3), specifically from January 13 – March 7, 2011,
grab sample measurements of chloride and sulphate were
purposely conducted with the aim of troubleshooting the
source of the chloride issues, and their measurements in
the HL tank (make-up supply) were respectively
0.3±0.7 µg · kg–1 and 6.3±1.5 µg · kg–1. In fact, the chlo-
rides, for all practical purposes, were non-detectable
within this period except on February 16, 2011, when only
a small value of 2 µg · kg–1 was recorded as an average in
the two HL tanks which are tied together as make-up.
However, chlorides of varying and higher amounts in either
post CEP and/or post HP heater #6 were observed. This
indicates different sources of chloride ingress, and these
are discussed in separate papers (Parts II and/or III) of this
series of chloride-contamination investigations. For
instance, for the February 16, 2011 sampling, with a rela-
tively higher sulphate concentration of 6 µg · kg–1 (than the
2 µg · kg–1 chloride) in the HL tank, the chloride and sul-
phate after both the CEP and the HP heater #6 were
7 µg · kg–1 and 0 µg · kg–1 respectively. Thus, although the
sulphate (and for that matter also the chloride) in the make-
up was to be diluted to the extent of not being detectable
in the feedwater (i.e. < 0.03 µg · kg–1 by calculations),
Author's Copy
appreciable chloride concentrations were measurable in
the feedwater. Unquestionably, the persistent chloride in
the feedwater must be coming from sources other than the
make-up. In fact, the results for that day may also be used
to support the elimination of the ammonia injection system
as a significant cause of the chloride issue as that should
have translated into a higher chloride concentration at the
downstream sampling spot (HP heater #6). However, there
were at least two occasions (February 28 and March 2,
2011) when with no detectable chloride in the HL tank
make-up water or the CEP water, 4.2 and 2.0 µg · kg–1 Cl–1
were respectively measured in the post HP heater #6 sam-
ples. This arguably could be coming from the ammonia
injection; however, it is also possible that it came from the
condenser in the form of some Cl-containing compound
(e.g. HOCl, haloacetic acids, THM or chloroamines) which
could be converted to chloride after the CEP. This second
idea forms part of the working hypothesis of Parts II and III
of this series of water/steam cycle investigations, which
will be published in separate papers.
Halo-organic Sources from WTP THMs can decom-
pose in the water/steam cycle to form chlorides [12]. A high
proportion of THMs has been observed to escape the
make-up water treatment plant [8], and they can also enter
the water/steam cycle through other routes [12]. Bursik, in
his article entitled "Carbon Is Not Equal to Carbon," puts
emphasis on organics as a more frequent cause of cycle
chemistry issues and lists them even above the well-
known causes of component failures such as flow-acceler-
ated corrosion (FAC), corrosion fatigue, stress corrosion
cracking (SCC) and hydrogen damage [11]. Total organic
carbon (TOC) is the common measure for organics in
PowerPlant Chemistry 2012, 14(2)
PPCHEM
treated make-up, and various limits, ranging from 100 to
300 µg · L–1 as carbon, have been arbitrarily set by organi-
zations such as EPRI, VGB and Eskom for make-up water
to the water/steam cycle [11,16]. Bursik however argues
that it is almost impossible to give generally applicable nor-
mal target values as organic compounds that enter the
plant cycle are different in many ways. He draws attention
to the fact that it is the presence of heteroatoms (e.g. halo-
gens, sulphur, and phosphorus) in the organics (measured
as TOC) that should be of major concern. Thus, whereas
100 µg · L–1 (EPRI's target for make-up TOC [15]) in the
form of a heteroatom-free organic compound may be rela-
tively harmless, it can be harmful in the form of, for exam-
ple, chloroform (CHCl3) [11].
Assuming a total decomposition of the organic com-
pound(s) and neglecting losses due to deaeration or blow-
down, a measured carbon content of 100 µg · L–1 (TOC) in
the make-up when the organic compound is CHCl3
(994 µg · L–1) would translate to a chloride concentration of
11 µg · L–1 in the boiler feedwater for a plant that operates
with similar make-up (2.46 kg · s–1) and steam flows
(198 kg · s–1) as this plant. And with the boiler operating at
both the water volume and conditions as in this plant, such
a level of chloride in the feedwater could lead to an
increase in chloride concentration in the boiler water of
~37 µg · kg–1 per hour (see Appendix A, method 1, for how
this was calculated). In practice, such a situation will call
for continuous blowdown (CBD) all the time to keep within
the cycle chemistry operating limits set by recognized
organizations such as EPRI (e.g. [6]). In a nuclear power
plant with "once-through" boilers and seawater-cooled
condensers that experienced on-load corrosion boiler tube
leaks from halide sources [8], THMs in the make-up water
were identified as a significant source of chloride and bro-
mide ions in the boiler feedwater (contributing
~0.3 µg · kg–1 halide in the feedwater). The measured chlo-
rine-containing THMs in their make-up water were
22 µg · kg–1 CHCl3, 20 µg · kg–1 CHCl2Br and 13 µg · kg–1
CHClBr2. For the operating conditions of the power station
under discussion in this paper and the assumptions made
above, such make-up THM levels will translate to
0.37 µg · kg–1 chloride in the feedwater and would lead to a
chloride increase of 1.2 µg · kg–1 per hour. This level of
ingress, if it pertained to the power station under discus-
sion, would be high enough to account for the chloride
contamination encountered as this would require blow-
down intervals of approximately 3–4 days due to chlorides.
At this power plant, however, the total THMs in the make-
up water were found to be less than the detection limit of
2 µg · kg–1 [17]. Assuming a total decomposition of the
THMs, neglecting losses due to deaeration or blowdown,
and assuming that the THMs in the make-up are essentially
composed of CHCl3 (which has the greatest number of Cl
atoms), then under the worst case scenario (i.e. = limit of
detection), a maximum chloride concentration of only
105
 PPCHEM Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I
~0.02 µg · kg–1 in the feedwater is expected from this
source. This translates to an increase of only ~1.8 µg · kg–1
per day (see calculation method 1, Appendix A) in chloride
levels in the boiler water. For such a level of chloride
ingress, ~46 to 63 days would be the required time interval
between chloride-based blowdown using EPRI's action
level 1 requirement [6] if the chloride concentration prior to
the ingress or at the end of each blowdown is kept within 0
to 30 µg · kg–1, as an example. Apart from THMs,
haloacetic acids (HAAs) in the boiler make-up water,
though not often mentioned, can also contribute chloride
to the water/steam circuit. Previously [17], 1.6 µg · kg–1
CCl3COOH, 0.8 µg · kg–1 CHCl2COOH, and < 0.5 µg · kg–1
CHBrClCOOH were measured in the make-up water of this
plant [17]. Taking the worst case scenario, the maximum
chloride concentration expected in the feedwater from
both THM and HAAs sources will be ~0.04 µg · kg–1 and will
cause a daily increase of ~3.3 µg · kg–1 Cl– in the boiler
water (i.e. a blowdown requirement every 25–34 days to
keep within EPRI's guidelines for "normal" operation). With
a significantly more frequent chloride-based boiler blow-
down than experienced (typically 7–10-day and in some
worse situations 3–5-day intervals between blowdowns)
with this scenario, THMs and HAAs from the WTP (though
Author's Copy
jointly fairly significant) were not regarded as the main
source or root cause of the observed chloride ingress.
Furthermore, the estimations made above are quite con-
servative, as some THMs will certainly be removed by the
deaerator. THM removal of between 30 and 60 % has been
reported [18]. However, due to some operational changes
made in the WTP just prior to the water/steam cycle chlo-
ride issues, this source was also investigated as a potential
source.
On December 4, 2008, a decision was made to switch the
operation of the carbon beds (which are upstream of the
mixed bed in the boiler make-up treatment train) from par-
allel operation to series operation [17,19], and as the chlo-
ride contamination issue started quite soon after this
operational change (January 19, 2009), this was consid-
ered as a potential source. With the isolation of the LL tank
(see above), the two beds which had been running in
series for over 2 years were switched back to parallel
operation and maintained so between March 2 to March
23, 2011. The water/steam cycle was monitored atten-
tively with particular reference to any significant drop in
chloride increases as compared to periods prior to and
after the switch (see Figure 3). Based on some daily grab
samples, the average daily changes in chloride, sulphate
and sodium in the boiler (excluding periods when the
boiler was being blown down or during start-up & shut-
down conditions) were as follows:
(a) Beds in series before switching to parallel
(February 3 – March 1, 2011):
28.1±18.1 µg · kg–1 Cl–1, 0.8±3.0 µg · kg–1 SO42–, and
14.4±40.4 µg · kg–1 Na+;
106
(b) Beds in parallel operation
(March 3–23, 2011):
23.4±20.7 µg · kg–1 Cl–1, 2.19±17.7 µg · kg–1 SO42–,
and 11.9±49.9 µg · kg–1 Na+;
(c) Beds in series after parallel operation
(March 24 – April 8, 2011):
14.6±37.6 µg · kg–1 Cl–1, 0.9±10.0 µg · kg–1 SO42–, and
11.9±33.2 µg · kg–1 Na+.
The minor differences (in the light of the significant stan-
dard deviations) observed during this change in operation
of the carbon beds could not account for the switch from
sulphate-based blowdown to chloride-based blowdown
observed in this plant.
Condenser Tube Water Leak When discussing the
events with colleagues within the plant and within the cor-
poration, or when consulting through the FOMIS platform,
the first suspect for the chloride contamination in the boiler
drum was condenser tube water leak(s) [9]. However, with
a significantly high sulphate to chloride ratio of (~6–7):1 in
the re-circulating cooling water, any condenser tube water
leak from the water box should somehow reflect this rela-
tive ratio also in the water/steam cycle even if only small
leaks occur. Sodium, for example, is typically more than
twice the concentration of chloride in the cooling water
system; hence any such potential water leak, however
small, should also reflect the relative amounts of these
parameters in the water/steam cycle. Figure 4 shows chlo-
ride and sulphate concentration changes in the boiler
together with sodium concentration in the condensate
return for a period directly preceding one occasion of unit
outage for condenser tube leak repairs. As illustrated in the
figure, the first indication of a condenser leak in this plant is
typically from the sodium levels in the CEP discharge
water. With respect to the boiler chloride and sulphate, the
sulphate to chloride ratio prior to the first indication of the
condenser tube leak averaged 0.13±0.02 and increased to
0.30±0.12 from the first period of indication of the con-
denser tube leak to when it became more obvious, at
which point the ratio escalated to 1.53. With a CBD of
about 3.5 L · s–1 after this obvious indication of the con-
denser tube leak, the sulphate to chloride ratio continued
to increase to ~3.3 (approximately 12 h after) and to ~4.7
(just before the outage to fix the leak). The increasing SO42–
to Cl– ratio reflects the increasing amount of the relatively
higher sulphate cooling water leak into the hotwell. As can
be seen from Figure 4, the sudden increase in CEP Na+
indicating the condenser leak coincides reasonably with
the increase of the SO42–/Cl– ratio in the boiler drum. There
are therefore many clear indications in this plant's opera-
tion that distinguish a condenser tube water leak from the
observed chloride-specific ingress, which had been
persisting since January 2009 and resulted in frequent
boiler drum blowdown. It is noteworthy that the Feb 21,
2011 condenser tube leak outage occurred when the LL
PowerPlant Chemistry 2012, 14(2)
 Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I PPCHEM

350 10

9
300
8
MW generated
Cl and SO4 Concentration [µg · kg –1 ]

250 Cl boiler 7
SO4 boiler

CBD Rate [kg · s –1]

CEP Na [µg · kg –1 ]
6
Unit Load [MW]

200 Na (CEP)
Boiler CBD
5
Indication of more obvious leak
SO4/Cl ratio
150
4

100 3
1st indication of
condenser leak 2
50
1

0 0
19-Feb 19-Feb 19-Feb 19-Feb 19-Feb 20-Feb 20-Feb 20-Feb 20-Feb
0:00 4:48 9:36 14:24 19:12 0:00 4:48 9:36 14:24
Date, Time in 2011

Figure 4:
Author's Copy

Unit load versus CEP sodium and boiler chloride and sulphate concentrations, and continuous blowdown (CBD) rate for
periods directly preceding (February 19, 2011, 00:00 to February 20, 05:00 am) and during a condenser leak episode
(after February 20, 2011, 05:00 am).

tanks were isolated from the HL tanks (the make-up supply of ammonia from different suppliers were dosed at different
tank). periods and attention was paid to the cycle chemistry, but
we could not confirm that the chloride ingress was due to
Condensate Pump Leak Chloride ingress into the contaminated ammonia. Although we have ion chromatog-
water/steam cycle from leakages via condensate pump(s) raphy (Dionex IC-DX-2000) to perform chloride analysis at
has been experienced by others, either as a leak at the low ppb levels, concerns about column damage from
base of the pump introducing stagnant water [9] or as ammonia, even in diluted solutions where the chloride lev-
leaks from condensate pump seal cooling water for the els were likely to be detected, made this prohibitive.
pump [10]. This was pursued, but there was no indication Furthermore, as the use of none of the different batches
that this was the likely source of the persistent chloride (including a supply from a previous source prior to the
ingress. chloride issue) alleviated the issue, there was not much
reason to pursue the analysis. An alternative approach was
NH3 Chemical Injection Contaminated ammonia sought to evaluate whether the cause of the chloride-
injected into the feedwater for pH control has also been based boiler drum blowdown was due to the ammonia
noted as a possibility, though it is less common [9]. This injection. From the suppliers' technical data sheet informa-
was perhaps the most confusing source to eliminate. It had tion, a maximum chloride amount of 1 mg · kg–1 can be
been initially noted that by switching the ammonia injection expected in any of the 28–30 % aqua ammonia dosed into
from one of the two ammonia dosing tanks to the other, the boiler. With a typical ammonia injection rate of only
some improvements were made in the boiler drum chem- ~5.1 mL · min–1, the expected increase in the boiler water
istry. However, a consistent switch from one tank to the chloride concentration from this injection source will be
other could not confirm this. Having changed vendors for only ~12 µg · kg–1 for an entire year of continuous operation
the supply of ammonia and with indiscriminate ammonia (see Appendix A, method 1, for the calculation). It was
dosing from the various supplies, the ammonia injection therefore concluded that the ammonia injection was not
was considered a suspect for the chloride ingress. responsible for the chloride-based blowdown. However,
Furthermore, our laboratory staff had noticed a higher the observation of a likely association of the problem with
requirement to dose more ammonia for pH control. With all ammonia injection will be discussed in more detail in sepa-
this in mind, the first step taken was to empty and clean rate papers as Parts II and Parts III of this series of chlo-
both ammonia dosing tanks (in stages). Different batches ride-contamination investigations.

PowerPlant Chemistry 2012, 14(2) 107

 PPCHEM Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I

CONCLUSIONS
Chloride is a well-known corrosive inorganic ion, which
can potentially cause or contribute to equipment break-
down, e.g. boiler tube and steam turbines failures. The
power plant unit discussed in this report was affected by
elevated chloride levels in the water/steam circuit, result-
ing in more than normal continuous blowdown of the
boiler to keep it in operation. The paper enumerates pop-
ularly known sources of chloride ingress into the
water/steam cycle and provides the bases on which these
were eliminated as root causes of the chloride crises.
These sources include the following: make-up water con-
tamination, feedwater contamination from sources such
as condenser tube water leaks and/or leaks from conden-
sate pump seal cooling water for the condensate pumps,
leakages from condensate polishers or via contaminated
chemical injections.
ACKNOWLEDGEMENT
We would like to express our gratitude to all the fellow
chemists at SaskPower for the helpful discussions. To the
Shand Power Station laboratory, operational and mainte-
nance staff, thanks for being part of the team in this effort
to identify the root cause of the chloride contamination. To
Blair Mowchenko (production specialist), Kevin Guillemin
(production supervisor), Kevin Scobie (plant manager) and
the others, we say thanks for all the fruitful discussions
and thought-provoking ideas. Special thanks also go to
Dwayne Selensky and Jackie Lam of the Chemical
Laboratory Division and Mahnaz Missaghi of the
Metallurgy Laboratory Division of the Chemical Services
Laboratory for the Operation Support Group of
SaskPower for performing laboratory analyses which were
instrumental in the general understanding of the issues
discussed in this paper. Lastly, we want to thank Rico
Tomsha for the excellent schematic drawing.

APPENDIX
Author's Copy

Determining the Cycling Rate in the Boiler and Specified Contaminant (X) Based Blowdown Frequency
Requirements

Nomenclature
B blowdown
–1
BR kg · s blowdown flow rate
BV L firing boiler volume (drum, waterwalls, headers, etc)
–1
BWX µg · kg contaminant concentration in the boiler water
–1
BX µg · kg contaminant concentration in the blowdown
–1
COC s cycle of concentration
F feedwater
–1
FR kg · s feedwater rate
–1
FX µg · kg contaminant concentration in the feedwater
–1
L kg · s steam losses
M make-up
–1
MR L·s make-up flow rate
–1
MX µg · kg contaminant concentration in the make-up
–1 –1
RX µg · kg · s rate of increase of the contaminant concentration in the boiler water
t s time
T s cycle duration
TBD d time required for the next blowdown
–1
TBWX µg · kg target concentration of the contaminant in the boiler water
X contaminant
W kg mass of water in a condensate return vessel

108 PowerPlant Chemistry 2012, 14(2)

 Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I
In water/steam cycle operation, there is generally an accu-
mulation of contaminants in the boiler and accumulation
of condensate (pure water) in the condensate return sys-
tem; in the absence of blowdown, the contaminant level in
the boiler will rise rapidly [20]. When operating within stan-
dard guidelines (such as those specified by EPRI as fol-
lowed for the operation of this unit), carryover of contami-
nants such as chloride in the steam is negligible or is
assumed to be negligible [6]; the boiler therefore acts as a
"sink" to accumulate ingress of such contaminants in-
between blowdowns. Therefore, occasionally, there is the
need to blow down some content of the boiler water,
which is replaced with fresh make-up to dilute the content
of the remaining soluble contaminants in the boiler to
within standard operational requirements. There are two
main reasons for blowing down from the boiler: intermit-
tent removal of suspended solid particles, where the take-
off is usually located at the bottom of the boiler drum, and
the continuous blowdown (CBD) of soluble contaminants
from locations of the highest dissolved solids in the boiler
drum [21]. As can be seen in the name, CBD is the contin-
uous removal of water from the boiler, but this can be
done automatically or manually, both of which is based on
the operating water quality criteria for blowing down [21].
Author's Copy
(The automatic blowdown system continuously monitors
the boiler water, adjusts the rate of blowdown, and main-
tains the specific conductance of the boiler water at the
desired level.) In this article, reference to CBD means the
latter and the CBD control valves are adjusted "manually"
from the control room according to laboratory grab sam-
ple test results to meet the specifications by EPRI to main-
tain good water/steam cycle chemistry. Thus, the CBD
operation for this unit can be said to be operated intermit-
tently instead of continuously.
For a water/steam cycle where some of the boiler water is
being blown down, the term cycles of concentration, COC
(used more commonly for cooling towers), is used to refer
to the number of times the minerals in the feedwater have
been concentrated in the boiler by its operation [22]. COC
can be defined both in terms of the relative flows and the
relative concentrations of the contaminant (X) in the feed-
water and the blowdown water as expressed in Eq. (1) [22].
(1)
Some properties required of X to make the equation valid
include zero or minimal carryover and high solubility in
water. Chloride, for example, exhibits these characteris-
tics, especially when maintained below the maximum level
permissible as in recognized operating guidelines by
organizations such as EPRI. Thus, for example, make-up
water with a chloride concentration of 5 µg · kg–1 and
boiler water with a concentration of 30 µg · kg–1 is said to
have boiler water at 6 cycles of concentration. However,
and without getting into technical details, the definition of
COC itself as in Eq. (1) suggests that the term is applicable
PowerPlant Chemistry 2012, 14(2)
PPCHEM
only under conditions when the boiler is being blown
down and hence is inapplicable for in-between blowdown
conditions. For in-between blowdown conditions, the
boiler serves as a sink to continuously increase the con-
centration. Cycles of concentration, if used here, would
likewise increase with time. Thus, modification of Eq. (1) is
required in predicting the cycling in the boiler under the in-
between blowdown conditions and this is addressed
below using different approaches.
Method 1A
This method can be used when the concentration of the
contaminant or parameter in the make-up or the feedwa-
ter and their respective flow rates are known. Based on
mass balance and treating the boiler as the main "sink" for
the ingress of the contaminant, an increasing amount of
the contaminant is expected with time. The rate of
increase of the contaminant (X) concentration in the boiler,
RX, can therefore be calculated simply (in make-up terms
for instance) as follows:
(2)
The time required (in days) for the next blowdown can be
calculated using
(3)
It is noteworthy that Eq. (2) can similarly be expressed in
feedwater terms (i.e. by replacing the make-up concentra-
tion and flow with the feedwater concentration and flow,
respectively).
Method 1B
Following Spencer et al.'s boiler model [20], the state of
the water/steam system is described by 2 variables only,
namely the mass of water in a condensate return vessel,
W, and the contaminant concentration in the boiler, BWX.
The infinitesimal change in these variables with time (by
expressing the flows in terms of the usual measurable
terms of volume/time instead of mass terms as by
Spencer et al. [20]) can be expressed in the following
differential equations:
(4)
and
or
(5)
109
 PPCHEM Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I
0 ≤ t ≤ T, where t is time and T is the duration of a cycle.
We focus on Eq. (5) as the relevant equation for this paper
and solve the differential Eq. (5) as follows:
(6)
In the absence of blowdown, as presented for Method 1A
above, the integral equation simplifies to
(7)
This yields Eq. (8) as the solution:
(8)
It has to be noted that Eq. (8) is the same as Eq. (2),
although different approaches were used to derive the
expression. Furthermore, the make-up terms can be sub-
stituted with feedwater terms to obtain the same result.
Method 2
Author's Copy
In the situation in which the parameter or contaminant of
interest can be measured accurately in the feedwater, a
modified method of the COC approach can be used to
determine a time-dependent concentration cycling
expression in the boiler for the ingress in the feedwater.
This is determined from the measurement of the BWX at
times t1 and t2 to obtain concentrations BWX,1 and BWX,2
(= ⌬BWX) as well as the feedwater concentration FX. The
COC is expressed per unit time (e.g. per second COC) as
follows:
(9)
Thus, an increase in the boiler drum concentration from
any particular time can be determined by multiplying the
projected time by the COC and by the feedwater concen-
tration (assuming it is constant). In cases where the con-
taminant concentration in the feedwater is unsteady (vari-
able), a weighted average of the feedwater concentrations
within the specified time intervals would have to be used
in Eq. (9) to determine the time-dependent COC. Similarly,
a weighted average would have to be used in determining
the increase in the boiler drum concentration of the con-
taminant if the feedwater concentration is variable.
Knowing the rate of increase of the contaminant in the
boiler, the time required for the next blowdown can be pre-
dicted as in Eq. (9) above.
110
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 Chloride Contamination of the Water/Steam Cycle in Power Plants – Part I PPCHEM

Steam/Water Circuits, 1980. CEGB North Western Jonathan P. Ruffini (B.Eng., Chemical Engineering, E.I.T.
Region Stockport, UK. (Engineer in Training)) started his engineering career at
SaskPower as an intern in 2010. After graduating from
[19] Quagraine, E. K., Proc., International Water Confer-
McMaster University, Canada, in 2008, Jonathan Ruffini
ence, 2011 (Orlando, FL, U.S.A.). Engineers' Society
did several different jobs before starting as an engineering
of Western Pennsylvania, Pittsburgh, PA, U.S.A.,
intern at the Shand Power Station, where he progressed
Paper #11-69.
to a chemical engineering position within SaskPower a
[20] Spencer, J. L., Connick, B. J., Filippi, A. J., Chemical year later with the Clean Coal Project. He had written one
Engineering Communications 1986, 47(4–6), 329. paper on the sequestration of carbon dioxide from a coal-
fired power plant before graduating.
[21] Handbook of Industrial Water Treatment, Chapter 13:
Boiler Blowdown Control. GE Power & Water, Power
& Process Technologies. Available at
http://www.gewater.com/handbook/boiler_water_sy
CONTACT
stems/ch_13_blowdowncontrol.jsp.
Emmanuel K. Quagraine
[22] Unified Facilities Criteria (UFC). Industrial Water
Shand Power Station
Treatment Operation & Maintenance, 2005. U.S.
P. O. Box 1310
Department of Defence, Washington, DC, U.S.A.
Estevan, SK, S4A 2K9
U.S.A., UFC 3-240-13FN, Chapter 3. Available at
Canada
http://www.wbdg.org/ccb/DOD/UFC/ufc_3_240_13f
n.pdf.
E-mail: equagraine@saskpower.com
Author's Copy

THE AUTHORS
Emmanuel K. Quagraine (B.S., Chemistry and Diploma in
Education, M.S., Analytical Chemistry, University of Cape
Coast, Ghana, Ph.D., Analytical Chemistry/Bio-inorganic
Chemistry, University of Saskatchewan, Canada) started
his career as an assistant lecturer at the University of
Cape Coast in 1993 and later became a lecturer and a
senior lecturer at the same university. Since April 2006, he
has been the supervisor of the Chemistry Laboratory and
Environmental Affairs for the Shand Power Station,
SaskPower. Emmanuel Quagraine previously also worked
as a sessional instructor at the University of
Saskatchewan and as an instructional associate at
Brandon University, Manitoba, Canada. He has various
post-doctoral experience including working with the
University of Saskatchewan, the National Water Research
Institute, and the WateResearch Corporation, all in
Saskatoon, SK, Canada, and with the Chemistry
Department of the University of Michigan, Ann Arbor,
Michigan, U.S.A. He has presented many papers at local,
national and international conferences and has authored
or co-authored several published articles in peer-reviewed
journals. He is currently a member of the American Water
Works Association (AWWA) and the Association of the
Chemical Profession of Ontario, Canada.

PowerPlant Chemistry 2012, 14(2) 111

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