Applied Thermal Engineering 59 (2013) 683e694

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Applied Thermal Engineering

journal homepage: www.elsevier.com/locate/apthermeng

Extensive feedwater quality control and monitoring concept for

preventing chemistry-related failures of boiler tubes in a subcritical
thermal power plant
Sonja Vidojkovic a, *, Antonije Onjia b, Branko Matovic c, Nebojsa Grahovac c,
Vesna Maksimovic c, Aleksandra Nastasovic a
a
Institute of Chemistry, Technology, and Metallurgy, University of Belgrade, Njegoseva 12, 11001 Belgrade, P.O.B. 473, Serbia
b
Laboratory of Chemical Dynamics and Permanent Education, “Vinca” Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522,
11001 Belgrade, Serbia
c
Laboratory of Material Science, “Vinca” Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, 11001 Belgrade, Serbia

h i g h l i g h t s

Feedwater quality monitoring practice in a thermal power plant has been evaluated.

The more efficient feedwater quality control have been applied.

Analysis of feedwater quality parameters has been performed.

Exceeded levels of corrosive contaminants were found.

Recommendations for their maintenance at proscribed values were given.

a r t i c l e i n f o a b s t r a c t

Article history: Prevention and minimizing corrosion processes on steam generating equipment is highly important in
Received 19 December 2012 the thermal power industry. The maintenance of feedwater quality at a level corresponding to the
Accepted 14 June 2013 standards of technological designing, followed by timely respond to the fluctuation of measured pa-
Available online 27 June 2013
rameters, has a decisive role in corrosion prevention. In this study, the comprehensive chemical control
of feedwater quality in 210 MW Thermal Power Plant (TPP) was carried out in order to evaluate its
Keywords:
potentiality to assure reliable function of the boiler and discover possible irregularity that might be
Thermal power plant
responsible for frequent boiler tube failures. Sensitive on-line and off-line analytical instruments were
Feedwater quality
used for measuring key and diagnostic parameters considered to be crucial for boiler safety and per-
formances. Obtained results provided evidences for exceeded levels of oxygen, silica, sodium, chloride,
sulfate, copper, and conductivity what distinctly demonstrated necessity of feedwater control
improvement. Consequently, more effective feedwater quality monitoring concept was recommended. In
this paper, the explanation of presumable root causes of corrosive contaminants was given including
basic directions for their maintenance in proscribed limits.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction efficiency, and diverse damages in other segments of power units.

Deposit formation and corrosion processes on heat exchange
surfaces significantly influence operational reliability of thermal
power plant boilers. Deposit of corrosion products on heat transfer
surfaces of thermal power plants can lead to heat transfer
decreasing, overheating and tube failures, loss of turbines
* Corresponding author. Tel.: þ381 60 696 8480.
E-mail addresses: sonjavidojkovic@chem.bg.ac.rs, sonja66yu@yahoo.com
(S. Vidojkovic).
So far, abundance of studies were published on boiler tube failures
caused by deposit formation on the inner wall surfaces in thermal
power plants. For instance, Ghosh et al. [1] confirmed that deposit
composed of silicates was responsible for the failures of boiler
tubes, Husain and Habib [2] proved that magnetite scale formation
on the inner surface of the tube induced its overheating and sub-
sequent rupture, and Saad Abou-elazm et al. [3] revealed high
concentration of sulfur, chlorine and oxygen within the cracks
caused by stress corrosion cracking. Aggressive chemicals can be
concentrated and accumulated under deposit and enhance the

1359-4311/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.applthermaleng.2013.06.028
684 S. Vidojkovic et al. / Applied Thermal Engineering 59 (2013) 683e694
corrosion processes provoking failure of tubes through various
corrosion mechanisms and metallurgical degradation generalized
by Dooley [4]. Accordingly, understanding and identification of the
mechanism of failure and root cause determination are main pre-
conditions for undertaking proper corrective actions and preven-
tion of repeated outbreaks.
In a new and clean boiler, a passive magnetite layer that grows
on inner metal surface provides corrosion protection. Under normal
operating conditions of power plant boilers, the protective
magnetite layer is formed as a result of reaction between steel (an
iron based-alloy) and deoxygenated water (or steam) according to
the following simplified reaction:
3Fe þ 4H2 O/Fe3 O4 þ 4H2
Intermediate compound in this process is ferrous hydroxide [Fe
(OH)2], which is transformed to the magnetite at temperatures
higher than 100  C, following the Schikorr reaction:
3FeðOHÞ2 /Fe3 O4 þ H2 þ 2H2 O
Formed metal oxide prevents contact between metal and
oxidizing ions and inhibits oxidation of metal. Magnetite film is
black colored, dense, adherent, tenacious, self-healing, and resis-
tant to temperature fluctuation. However, under unfavorable con-
ditions, magnetite film is susceptible to damage or breakdown that
eventually results in corrosion of the basic metal. Recently made
examination of the failed feedwater tube, demonstrated by Hen-
derson and Brazil [5], provided evidence on the strong corrosive
attack and cracking of metal as a result of the loss of protective
oxide layer. Crucial factor that can affect protective layer is
disruption in feedwater chemistry. Thus, magnetite, which is the
commonly protective corrosion product, gets porous and brittle
features that might have boiler tube an adverse effect on tube
surface protection.
Deposition and corrosion are main cause of efficiency loss in
power industry that has huge economic consequences. The results
of the Electric Power Research Institute study [6], that estimated
cost caused by corrosion in the electric power industry, indicated
that the total cost of corrosion damage involving deposition in the
water/steam cycle amounts US$1.9  109 what is 40% of the total
cost of corrosion in fossil power plants in the USA. The boiler tube
failures are the number one corrosion item with US$1.1  109
annually and reduce unit’s availability, reliability, and performance.
According to the data summarized by Chew at al. [7] they were
identified to be the vital factors which affect the practical imple-
mentation of heat integration in the industry that became a well-
established strategy for energy conservation involving heat ex-
changers, design of thermal process, power systems and control as
described [8], and initiating the development of advance tools for
determination of sensitivity of heat integration methodology as
shown [9]. Economic factors connected to the conventional power
systems urged development of efficient numerous techniques for
optimal power allocation and determination of storage capacity
targets in a hybrid power system including renewable energy
sources as presented [10].
According to accessible data, around 60% of damages of power
plant equipment occur due to deviation from the normal water
chemistry. In addition, corrosion and deposit in the steam/water
circuit of thermal power plants lead to a rise in the cost of the
electric energy. For that reason, the quality of water has to be
optimized for minimizing the content of contaminants to meet
criteria of design and operation of the boiler.
The feedwater system is the main source of corrosion products
and other corrosive impurities. They flow into the fossil boiler, form
deposit and enhance corrosion processes on the heat-transfer
(1)
Fig. 1. Internal surface of economizer.
surfaces of the entire water/steam cycle. The most important
(2) aspect of boiler feedwater preparation is its quality control. The
purpose of good feedwater control is to prevent and/or reduce
corrosion in boiler system and to minimize the transport of
corrosion products and corrosive contaminants to the boiler.
Operational experience of modern fossil power plants shows that
even strict abidance to impurity limits in feedwater does not pre-
vent deposition of corrosion products and other compounds in
boiler tubes. Boiler feedwater quality parameters depend on
design, metallurgy and physical parameters of a specific boiler
(temperatures, pressures, etc.), and type and operational mode of
the plant (base, medium or peak load operation) as well.
Numerous shutdowns caused by deposit and corrosion damages
were the reason for increased attention to feedwater chemistry in a
210 MW subcritical power plant that was object of investigation
described in this paper. The survey of boiler records showed that
considerable number of shutdowns has been caused by boiler tube
failures, which occurred between 2 and 20 times per year from its
commissioning. In the last ten years tendency for shutdowns to
increase was evident. Likewise, the recent examination of the boiler
tube system discovered destruction of protective magnetite layer
and various corrosion damages, including stress corrosion cracking
and pitting corrosion, on water side of economizer (but also other
parts of boiler tubes) which was covered by brown/reddish, scaled,
scabrous and bulging deposit layer (Fig. 1).
Taking into account that feedwater is a boiler operation me-
dium, which can directly affect metal surface, and the most
responsible factor for purity of water/steam circuit, emphasis in
this paper was placed specifically on its quality and possibility to its
improvement. Within the water/steam cycle evaluation, an exten-
sive analysis of feedwater has been conducted and large number of
parameters has been analyzed in order to investigate whether
water quality ensures reliable operation of boiler and identify
possible deviation in water chemistry that may be responsible for
frequent boiler tube failures. Obtained results give important in-
formation about existing water/steam cycle, feedwater monitoring
efficiency, and direction for its optimization and provide data for
managing power plant reliability.
2. Steam generation process in a thermal power plant drum
boiler
The observed boiler is coal-fired, with steam reheating and
natural circulation of the boiler water. It was operated 19871 h. The
tube was made of steel St.45.8 DIN 17175.
Technological principle of steam generation in the boiler is
following (Fig. 2): feedwater, that is the heat transfer fluid with the
 S. Vidojkovic et al. / Applied Thermal Engineering 59 (2013) 683e694 685

Fig. 2. Simplified Scheme of the Power Chemistry Cycle for a Drum Unit on All-Volatile Treatment. 1 e feedwater; 2 e saturated steam in the boiler drum; 3 e superheated steam;
4 e reheated steam; 5 e condensate.

temperature, t, of 240  C and pressure p, of 16.8 MPa, is perma- Table 1. The conductivity, pH, and dissolved oxygen were moni-
nently being pumped into a boiler in order to balance the steam tored on-line using existing instruments in power plant. For pH
production. Economizer is a first heat transfer section in boiler that measurement on-line instrument, Yokogawa PH402G has been
heats feedwater to t ¼ 332  C, close to the boiling temperature; exploited. The conductivity has been measured by an on-line
having passed through economizer, water goes to the drum which conductometer Yokogawa SC402G. Measurement of dissolved
separates steam from water producing saturated steam. Saturated oxygen has been performed using an on-line electrode Yokogawa
steam is delivered to the superheater which heats it to t ¼ 5405  C DO202G (S). In order to determine content of silica UV/VIS
and p ¼ 13.7 MPa turning it into superheated steam. Eventually, Spectrometer Perkin Elmer Lambda 40 has been applied. The
superheated steam is directed to the high pressure turbine. concentration of iron and copper has been measured by means of
Afterwards, the water/steam cycle carries forward through the Perkin Elmer 4100 ZL. TOC measurements were made by Astro
following path: after high pressure turbine steam is reheated to Lab TOC Model 2100. For sodium cation (Naþ), and the chloride
t ¼ 535  C, p ¼ 12.7 MPa. Having passed through intermediate and and sulfate anions (Cl-, SO2-
4 ) concentrations ion chromatograph
low pressure turbines it is expanded up to t ¼ 33  C, p ¼ 0.0049 MPa Dionex DX-300 was utilized. The instrument consists of an
and moves ahead to condenser. Condensate is transported by advanced gradient pump and CDM-3 conductivity detector. The
condensate pump, through condenser polisher, to the low pressure employed analytical separation column for cations was Dionex
heaters and deaerator where deaeration process is accomplished. IonPacÒ-CS 12A, preceded by a Dionex IonPacÒ-CG12A and for
From deaerator water is carried, by feedwater pump, to the high anions was a Dionex IonPacÒ-AS14 preceded by a Dionex Ion-
pressure heaters where it is heated to a temperature of 240  C and PacÒ-AG14 guard column. Columns were made of the same
subsequently injected in the boiler. polymer resin for anion exchange. An Anion Self Regeneration
The boiler feedwater in present TPP originates from the river. Suppressor (ASRS ultra) was used. Dionex Peaknet ver.5.1 soft-
This water is chemically prepared in the chemical water treatment ware was employed for instrument control, data collection and
plant where is demineralized, sent to demineralized water tank and
than supplied to the condenser outlet. In such a way, demineralized
water is employed as a compensation for the loss of condensate in Table 1
The techniques and instruments used for experimental investigation.
the system and together with condensate is treated in condensate
polisher. Parameter Technique Instrument Sensitivity
For chemical conditioning of feedwater, reducing all-volatile pH Eletroanalytical Yokogawa PH402G 0.01 pH
treatment (AVT(R)) is applied which involves the addition of Conductivity Eletroanalytical Yokogawa SC402G 0.01 mS cm1
ammonia, as alkalizing, and hydrazine, as reducing agent. Dissolved O2 Eletroanalytical YokogawaDO202G (S) 1 ppb
Silica, SiO2 UV/VIS Spectrometer Perkin 1 ppb
Elmer Lambda 40
3. Experimental analysis Sodium, Naþ IC Dionex DX-300  0.1 ppb
Chloride, Cl- IC Dionex DX-300  0.1 ppb
3.1. Techniques and instrumentation Sulfate, SO2-
4 IC Dionex DX-300  0.1 ppb
Iron, Fe GF-AAS Perkin Elmer 4100 ZL  0.1 ppb
Copper, Cu GF-AAS Perkin Elmer 4100 ZL  0.1 ppb
The techniques and instruments, along with their sensitiv- TOC NDIR Astro Lab TOC Model 2100 0.1 ppm
ities, used for experimental investigation are presented in
686 S. Vidojkovic et al. / Applied Thermal Engineering 59 (2013) 683e694

processing. A Spectra-Physics model AS3500 autosampler was according to standard procedure. The water samples were stored in
used for the direct programmed injection of samples. polypropylene bottles and transported in a portable refrigerator to
On-line instruments yield continuous record of water condition the laboratory where analyses were performed. Pre-treatment was
and enable direct control of operational chemistry, prompting not prerequisite excluding filtering for the IC measurement.
appropriate action. They operate using Ion Selective Electrode (ISE).
Off-line analytical techniques produced additional diagnostic in- 4. Results and discussion
formation. Principally, the intervals of analysis may vary according
to the urgency of action required based on the results. In the course of boiler feedwater quality monitoring measure-
For off-line feedwater analysis, the succeeding analytical tech- ments of representative samples of feedwater have been performed
niques were utilized: every third month. The results for the key and diagnostic param-
eters, obtained for the period of one year, are presented in Tables 4
-Ion Chromatography (IC) for the concentration of Naþ, Cl- and and 5, respectively.
SO2-
4 The values of particular parameter are discussed below:
-Graphite Furnace Atomic Absorption Spectrometry (GF-AAS) pH: in order to minimize the corrosion rate of both carbon steel
for iron and copper concentration and copper allows the target value under reducing conditions in
-Spectrophotometry (UV/VIS) for silica (SiO2) content feedwater system should be maintained within the range of 9.0 and
-Non-dispersive infrared (NDIR) for total organic carbon (TOC) 9.3 according to the widely used guidelines [13] on the cycle
chemistry for fossil plants, that have been developed by specialists
from Electric Power Research Institute (EPRI) of the United States to
3.2. Samples and preparation achieve benefits of reducing boiler tube failures and make a sub-
stantial progress in improving unit availability and reliability. Based
In this work, the sampling points appertaining to the feedwater on design specification, pH interval for investigated boiler is iden-
system have been considered. Feedwater is monitored at Econo- tical. However, the obtained results on pH values in EI (Fig. 3)
mizer Inlet (EI), Deaerator Outlet (DO) and additionally in showed certain deviation and varied between 8.20 and 8.57
Condensate Polisher Outlet (CPO). Sampling points at these loca- (Table 4). It can be attributed to inappropriate conditioning with
tions are shown in Table 2 Sampling point in Deaerator Inlet (DI) ammonia. Regular monitoring of pH in actual power plant involves
was not in function. on-line measurement and daily off-line control in EI. Overview of
For the feedwater quality monitoring two groups of parameters power plant data for previous year showed that pH value was not
are measured: key parameter (essential for adequate control of the fairly stable and fluctuated between 8.8 and 9.4. A representative
cycle chemistry) and diagnostic parameters (provide diagnostic diagram on pH vacillation with the time for a period of one month
data and further information that enable evaluation of possible is shown in Fig. 4. Decreasing of pH causes increase of corrosion rate
disruption in water/steam cycle). The key parameters for feedwater and intensifies dissolution of magnetite protective layer. In an
in tested power plant were: pH, conductivity, oxygen, and silica. overview [11] of the content of the fourth revision to the EPRI cycle
The diagnostic parameters were: sodium, chloride, sulfate, iron, chemistry guidelines the significance of maintaining elevated pH
copper and TOC. Explanations for monitored parameters, influence for protection against corrosion was stressed. Installing an auto-
to corrosion development and purpose of their measurements are matic ammonia dosing can considerably stabilize ammonia level in
given in Table 3. feedwater. Also, attention should be paid to the condenser leakage
Dissolved oxygen, conductivity, and pH were measured on line. as well as possibly insufficient removal of CO2 in deaerator. Ob-
Remaining measurements were carried out in the Institute of Nu- tained results for pH value in CPO were closely to expected range
clear Science “Vinca” using off-line (grab sampling) analysis. Off- and amounted to 6.70e7.70.
line analyses were made fast and handling with samples was Cation conductivity: represents conductivity of a water sample
careful in order to evade contamination. The sampling was made after passing through a strongly acidic cation exchanger in the
hydrogen form that removes all cations (like ammonia, sodium,
Table 2 potassium) and emits Hþ-cations. Accordingly, it reflects sum of
Sampling points in the feedwater system. cation conductivities that comprises conductivities of individual
anions and carbon dioxide coming from air in-leakage. According to
Sample point Parameters Rationale for sample points
the EPRI guidelines for feedwater [13], then to the new upgraded
Key Diagnostic technical guidance document related to the steam/water circuit of
Condensate Polisher Cation Chlorides
Control the effectiveness of fossil plants, authorized by the International Association for the
Outlet (CPO) conductivity the condensate polishers Properties of Water and Steam [18], and actual plant norms, the
Silica Sodium
Determination the need
value of cationic conductivity has to be lower than 0.2 mS/cm.
of polishers for
regeneration However, the measured conductivity was much higher than rec-

Evaluation of resin ommended: 0.52e2.52 mS/cm in EI and 1.24e2.65 mS/cm in CPO
particle “throw” from (Table 4). It can be ascribed, in good part, to the presence of chlo-
the condensate polishers ride, sodium, and significant amount of sulfate in the feedwater.
Deaerator outlet Dissolved
Evaluation of deaerator
oxygen performance
Diagrams of the cation conductivity dependence on the concen-
Economizer Cation Sodium
Control whether trations of chloride and sulfate within the ranges from 0 to 200 mg/
inlet (EI) conductivity Chlorides requirements by the boiler kg and 0e300 mg/kg, respectively, presented by Bursik [19], indicate
Sulfate manufacturers are met a considerable increase of cation conductivity with concentration of
Iron in terms of feedwater
chloride and sulfate. Changing of cation conductivity in EI during
Copper chemistry restrictions
TOC
Direct measurement of the investigated period is presented in Fig. 5. Along with impair-
total contaminant ingress ment of feedwater quality due to the raising of chlorides and sulfate
to the boiler contents, the increase of cationic conductivity is observed. In the

Monitoring oxygen and last two measurements concentrations of chlorides and sulfates in
pre-boiler corrosion
EI were exceptionally high (95 and 94 ppb of chloride and 130 and
 S. Vidojkovic et al. / Applied Thermal Engineering 59 (2013) 683e694
Table 3
Rationales for measured parameters in feedwater system and causes of their possible deviation.
Parameter Influence to the metal
pH
Corrosion of metals and alloys depends on pH [11] and
increases at lower pH

In alkaline environment solubility of protective magnetite
layer decreases and it has larger stability [12]
Cation conductivity
Increasing conductivity in water samples develops
corrosion processes, particularly in presence of oxygen.
Dissolved oxygen
Elevated concentration of oxygen combined with ionic
contaminants (especially chlorides) promotes acidic corrosion

Extremely low concentration of oxygen amplify flow-
accelerated corrosion and iron transport
Sodium
Sodium forms sodium hydroxide and sodium chloride that
cause corrosion of metal particularly in connection with
stress corrosion cracking

Sodium can also be present in form of soluble salts like
Na2O$Fe2O3$4SiO2 and Na2O$4CaO$6SiO2$H2O that deposit
on metal surfaces
Silica
Carried in by feedwater, silica is characterized by settling on
boiler tubes, and subsequently turbine in form of silicates
deposits (e.g.SiO2, Na2SiO3 $9H2O, NaFeSi2O6, Mg6[(OH)8Si4O10])
that are not soluble in water and extremely difficult for removing

Silicate deposit are responsible for losses in turbine
efficiency and capacity

Silica can enter in the feedwater in colloidal form, thus stay
undetected and afterwards have higher concentration in boiler
water and steam than permitted

Silica is the first impurity which passes through
an ion-exchanger if it requires regeneration
Chloride
Causes boiler tube failures from acid chloride attacks and
easily goes over in the steam initiating turbine failures from
chloride stress corrosion of turbine blades [13]

Chloride ion is exceptionally reactive and contributes
also pitting corrosion, hydrogen damage in boilers, corrosion
fatigue on turbine, and accelerates diverse corrosion processes [14].
Sulfate
Sodium sulfate stimulate development of general and local corrosion
processes primarily in high temperature medium

Sulfates as sodium sulfate form deposit on heat exchange surfaces
which leads to pitting during non-protecting shutdown periods

Acid sulfate can induce corrosion of boiler tubes
Iron
Corrosion products form deposit on internal tube walls,
concentrate impurities, produce corrosion fatigue, hydrogen
damage, and other forms of local corrosion, that result in
overheating and rupture of tubes.
Copper
Copper oxides behaves as oxidizers and source of oxygen

Dissolved copper transported from the feedwater system,
deposits in the high pressure turbine causing loss of turbine
efficiency and capacity [15]
Total organic carbon (TOC)
Thermal decomposition products of organics in feedwater can
produce corrosion damages on the boiler tubes and further, cause
foaming in the boiler, mechanical carryover and corrosion on
turbine [16]

As a result of decomposition process in the boiler organics can
form acetic acids and carbon dioxide [17] but also other organic
acids like formic, butyric, and propionic acid that are detected by
increased cation conductivity

Organic acids decrease pH that can be highly detrimental for
constructional material

Organics can foul ion exchange resins [16]

Hydrochloric acid is degradation product if organic impurities
consisting of chlorine
687
Purpose

Serves as an indication of all acid and basic
compounds and products of their reactions in water

Allows control of dosing regime (ammonia and hydrazine)

Reflects the salt content in the water alkalized
with ammonia

Control of regularity of water treatment plant and
condenser polisher function

Effective method for indicating the onset of leakage from
condenser pipes

Permits oxygen control of feedwater what
enables controlling material corrosion in feedwater system

Controls oxygen added for eliminate overdosed reducing
agent which speeds flow-accelerate corrosion up

Makes possible assessment for effectiveness of deaeration

Serves as indication of air in-leakage into the cycle

Precludes oxygen breakthrough into the system

Provides information of condenser leakage

Makes possible the estimation of conditioning quality

Provides control of condensate polisher performances

Enables evaluation of amount of deposited
soluble compounds

Points out a quality of feedwater

Indicates the impurity ingress that are typical due to
cooling water

Ensures maintaining of requested
concentration of silica in the feedwater
and condensate polisher outlet

Gives evidence of feedwater purity

Indicates efficiency of condenser polisher

Controls maintenance of permissible
concentration of sulfates in feedwater

Records presence of ion exchange resins
leaked in water from condensate polisher

Supplies information on the metal dissolution
process in the system, corrosion product levels
in feedwater and possible deposits in the boiler

Keeps iron within proscribed limits

Estimates the accuracy of water chemistry
control (reducing agent, ammonia, oxygen,
pH) and thus, provides maintenance of
satisfactory corrosion rate level

Indicates efficiency of conditioning

Serves as indicator of copper concentration
in feedwater enabling to maintain it in
allowed limits

Makes it possible to predict deposit in the
boiler and later in the turbine and gives
information regarding the metal dissolution

Checks correctness of water chemistry
control (ammonia, pH, oxygen)

Warns of in-leakage contaminants and
informs about troubleshooting problems
688 S. Vidojkovic et al. / Applied Thermal Engineering 59 (2013) 683e694

Table 4
The results obtained for key parameters in feedwater.

Feedwater quality Sampling points

parameters
Economizer Condensate Deaerator
inlet polisher outlet outlet

pH 8.38 6.70
8.57 7.70
8.20 7.70
8.31 6.70
Cation conductivity, mS cm1 0.92 1.24
0.52 1.37
2.17 2.24
2.52 2.65
Dissolved oxygen, ppb 9
22
31 Fig. 3. The obtained pH values in EI and CPO.
80
Silica, ppb 7 2
10 10 conspicuous leap of oxygen concentration in DO (Fig. 6). Recorded
10 16 concentrations were 1.6 and 4 times beyond current limit in TPP.
39 10.5
Oxygen breakthrough into the water/steam circuit indicates
Bold entries represent exceeded target values of measured parameters. possible defect in deaerator functioning and entails recondition of
sampling point in deaerator inlet in order to enable regular control
148 ppb of sulfate) what necessarily led to cation conductivity of its effectiveness. Review of power plant reports has confirmed a
upgrowth from 0.52 in the first measurement to 2.52 mS/cm in the frequent oscillation of oxygen content for a long period of time.
latest sample. Similar trend pertains to the CPO where cation Typical changes of oxygen concentration for a period of one month
conductivity was rising from 1.24 to 2.65 mS/cm. Presence of cor- are presented in Fig. 4. Oxygen is highly corrosive element and
rosive ions is considered below. Likewise, the condenser leakage can cause severe damages in steam generation tubes. Regular
should be checked and forestalled. Increasing of conductivity pro- control of the dissolved oxygen content in power plant comprises
motes corrosion processes particularly in presence of oxygen. It on-line monitoring in DO and weekly off-line measurement in
ought to be mentioned that power plant wields, except on-line for DO and EI. For removing residual oxygen, conditioning with hy-
continual, laboratory conductometer for daily monitoring as well, drazine is employed. The reaction between hydrazine and oxygen is
which give confirmation of the validity of on-line results. expressed as follows:
Dissolved oxygen: recommended target value in EI is below
5 ppb according to EPRI [13] but also VGB feedwater guidelines of a N2 H4 ðaqÞ þ O2 ðgÞ/N2 ðgÞ þ 2H2 O (3)
joint European Technical Committee [12], and below 10 ppb based
Hydrazine also passivates oxidized areas of boiler tubes ac-
on the IAPWS guidelines [18]. Dissolved oxygen limit in actual TPP
cording to following equation:
is 20 ppb. The oxygen content during investigation period was not
within proscribed values and amounted between 9 and 80 ppb N2 H4 ðaqÞ þ 6Fe2 O3 ðsÞ/4Fe3 O4 ðsÞ þ N2 ðgÞ þ 2H2 O (4)
(Table 4). The results of the third and fourth measurements showed
However, handling with hydrazine should be precautionary and
Table 5 safe because of its hazardous feature and carcinogen effect. The
The results obtained for diagnostic parameters in feedwater of TPP. latest cancer study in humans [20] distinctly confirmed the sig-
nificant increase the risk of cancer due to exposure to hydrazine. A
Feedwater quality Sampling points
parameters, ppb recent experimental investigation made in a thermal power plant
Economizer inlet Condensate polisher outlet
with mixed metallurgy [21] confirmed merits of carbohydrazide
Sodium 10 20 (N4H6CO) with ammonia and ethanolamine mixture as the most
30 40 convenient combination for substitution of hydrazine because of its
75 28
12 22
detrimental effect to the human health.
Chloride 40 42 Moreover, authors reported the data on decrease of oxygen, iron
90 80 and copper contents in feedwater and reduction of deposit amount
95 61 on boiler tube inner surfaces as a result of the carbohydrazide
94 82
application. Obtained results are rather valuable and provide a basis
Sulfate 30 10
20 10 for the development of new guidelines for the optional feedwater
130 130 chemical treatment. This approach could be also considered in the
148 119 context of the cleaner production that became a significant part of
Iron 2.7 4.2 the energy sector as explained by Klemes [22].
0.5 7.5
3 16
High concentration of oxygen causes corrosion pits that may act
5.5 6.3 as initial location for stress corrosion, so it is necessary to prevent
Copper 1.5 2.5 excessive concentration of oxygen in feedwater. In order to keep
5.3 <0.5 oxygen in harmless concentration deaeration has to be properly
12 <2
conducted and condenser leakage should be controlled and
3.1 3.2
TOC <300 <300 prevented.
<300 <300 Silica: technical specification for observed boiler requests silica
<300 <300 content in feedwater to be below 20 ppb. The acquired values for
<300 <300 the content of silica were mostly satisfactory and amounted to 7e
Bold entries represent exceeded target values of measured parameters. 10 ppb in EI and 2e16 ppb in CPO (Table 4) except for one sample
 S. Vidojkovic et al. / Applied Thermal Engineering 59 (2013) 683e694 689

Fig. 4. Change of the pH value and dissolved oxygen concentrations with time in EI for a period of one month.

taken in EI where silica was 39 ppb which is considered as very high
concentration (Fig. 7). EPRI [13] and VGB [12] guidelines propose
less concentration of silica in CPO which should not go beyond
10 ppb and 5 ppb, respectively. Unit is equipped with silicometer
for on-line measurement in feedwater and spectrophotometer for
daily surveillance of silica concentration. Review of power plant
records on silica content for three previous years confirmed its
frequent springs beyond the limited values. The highest reported
concentration was 174 ppb (Fig. 8). Restriction in silica concentra-
tion is very important due to thick and dense deposits formation on
the boiler and turbine surfaces that lead to thermodynamic and
mechanical loss of efficiency. Anionic exchanger is utilized to
remove dissolved silica. Slipping silica from the exhausted anion
exchange resin can cause its increase in feedwater. Therefore,
improvement of operation of water treatment plant and condenser
polisher is of great importance for maintaining silica in innocuous
limits. Taking action for preventing the ingress of cooling water is
also necessary for debarring silica presence from feedwater. In
addition, employing recently developed method [23] for simple
estimation and prediction of silica carry-over and solubility in the
steam can enable faster taking actions for deposition prevention
and presents easy approach of practical consequence for chemical
personnel.
Sodium: measurements showed that the concentration of so-
dium in EI varied between 10 and 75 ppb and in CPO between 20
and 40 ppb (Table 5), that it is above normal value in feedwater.
According to the guidelines developed by The International Asso-
ciation for the Properties of Water and Steam [18] recommended
target value for sodium in CPO is below 3 ppb. EPRI guidelines [13]
consider the target value for sodium in EI and constrained it to be
below 3 ppb. Elevated concentration of sodium in feedwater,
particularly in the second and third analysis (Fig. 9), indicates
contamination with NaOH, which is used for the regeneration of
the anion exchanger in condensate polisher. These concentrations

Fig. 5. Changes of cation conductivity during the investigated period.

690 S. Vidojkovic et al. / Applied Thermal Engineering 59 (2013) 683e694
Fig. 6. The obtained results for concentrations of dissolved oxygen in DO.
in EI were even 10 and 25 and in CPO 16 and 9.3 times higher than
recommended. Current condition is detrimental for boiler tubes,
and contributes corrosion processes. Furthermore, sodium com-
pounds such as sodium chloride (NaCl) and sodium hydroxide
(NaOH) are easily introduced in the steam path from the boiler and
inflict enormous damage on the turbine. Sodium hydroxide is
transported to the steam mainly as a mechanical carry-over
that involves mechanical transport of dissolved solutes present in
small droplets through the vapor phase. Sodium should be main-
tained within proscribed limits by proper regeneration and func-
tioning of water treatment plant and condensate polisher, and
controlling their effectiveness by installation on-line sodium-me-
ter. An advanced newly developed technology for on-line sodium
measurement [24] enables minimal reagent consumption, facile
maintenance, automatic calibration and measuring also grab sam-
ples. It is based on a combination of an electrode system that
measures pH and sodium.
Chloride: common practice at tested TPP, was to monitor chlo-
ride in EI on-line indirectly by measuring conductivity after the
sample that had been passed through a cation column, and daily in
CPO by grab sampling. However, since conductivity is a non-specific
measurement, it was difficult to accurately measure low concen-
trations of chloride. The EPRI guidelines [13] recommend chloride
content to maintain below 3 ppb in demineralized water, and
bellow 2 ppb in steam. In framework of extensive control of feed-
water quality the measurements of chloride content was accom-
plished in EI and CPO. Results showed that concentration of
chloride was extremely high in all of the analyzed samples and
amounted between 40 and 95 ppb in EI, and 42 and 82 ppb in CPO
(Table 5). The concentration of chloride is vastly higher than normal
value and does not provide reliability of boiler. Measured concen-
trations of chloride in EI and CPO are presented in Fig. 9. It may be
noted that its concentrations in EI during investigated period were
Fig. 7. The content of silica in EI and CPO.
13e32 times higher than recommended. Measurement on chloride
concentration in CPO showed similar deviation. The impact of
chloride ingress into the feedwater can potentially be very
damaging. A detailed experimental investigation, performed on a
modern high-temperature water loops [14], proved that in
oxygenated high-temperature water (T ¼ 288  C and a dissolved
oxygen content of 8 mg/kg), the addition of 10 mg/kg to 50 mg/kg
chloride to low-alloy steel reactor pressure vessels resulted in ac-
celeration of stress corrosion cracking. Neutral compounds of
chloride present usually in feedwater are hydrochloric acid (HCl) as
a predominant form, then ammonium chloride (NH4Cl) and sodium
chloride (NaCl). Hydrochloric acid exhibits relatively high volatility
and easily goes to the steam. Volatility of ammonium chloride is
lesser while sodium chloride has a minimal volatility as described
in the EPRI guidelines [13]. It should be mentioned that volatile
carryover is mechanism where solutes are distributed between
liquid and vapor phases as dissolved species at high temperature.
High concentration of chloride gives strong evidence that main
source of feedwater contamination is HCl that are reagent used for
the regeneration of the resins in Condensate Polisher. Likewise,
make-up water contamination and condenser tube leaks should
not be excluded as possible additional sources of contamination.
Chloride content in feedwater can be reduced, in the first place, by
proper regeneration and correct exploitation of polishing and water
treatment plants. Also, continuous on-line monitoring by chloride-
meter in CPO and daily laboratory analysis of chloride of demi and
feedwater water by ion chromatograph should be introduced in
regular power plant operation.
Sulfate: EPRI guidelines [13] specified target value for sulfate
below 3 ppb pertains to demi water only. During the investigated
period concentration of sulfates was too high and amounted 20e
148 ppb in EI and 10e130 ppb in CPO (Table 5). The last two sam-
ples taken from EI exhibit a sharp rise of sulfate concentration
which comes up to 130 and 148 ppb in third and fourth analysis,
respectively (Fig. 9) Similar results were obtained for CPO where
the third and fourth analysis also revealed enormous concentration
of sulfate amounted 130 and 119 ppm, respectively. This tendency
indicates a considerable deterioration of operating conditions
and requires exigent action of power plant personnel. The main
sources of sodium sulfate are condenser leakage and water treat-
ment plants where ion exchange resins are used. Namely, small
fractions of ion exchange resins can be imported in feedwater from
condensate polisher and subjected to thermal decomposition at
elevated temperatures that result in forming sulfate. Degradation of
ion exchange resins in thermal power plant environment can take
place through several fundamental mechanisms studied by Fisher
and Burke [25] and later examined by Hoffman and Aspden [26]
with particular emphasis on its implication on the plant design
and operation. The anion resin in condenser polisher has a vital role
in removing sulfate ion. The results also suggested that ion chro-
matograph should be regularly used for weekly analysis of sulfate
ions concentration. Likewise, results of Advanced MicroLabs, LLC
(AML) [27] on testing of the newly developed highly sensitive
analytical system for simultaneous on-line monitoring of trace
levels of chloride and sulfate based on microchip capillary elec-
trophoresis, gives new possibilities for keeping these anions in
secured limits.
Partition coefficient enables to predict behavior of impurities in
water/steam cycle of power generating units. In a comprehensive
experimental study conducted in Oak Ridge National Laboratory
(ORNL, USA) [28] the first data on the partition coefficient were
obtained in which allowance was made for the diverse forms of
sulfate. The results are interpreted in terms of thermodynamic
partition coefficient taking into account the activity coefficients of
species in the liquid and vapor phases, which is different from the
 S. Vidojkovic et al. / Applied Thermal Engineering 59 (2013) 683e694 691

Fig. 8. Change in the content of silica with time in EI for a period of one month.

conventional partition coefficient. The thermodynamic partition of ammonia (NH4OH). Furthermore, experiments were performed
coefficient of sodium sulfate and products of its hydrolysis, taking on a dynamic test rig that was entirely simulated processes taking
into account forms of sulfate, was determined as follows: place in a thermal power plant with drum boiler. It was proved that
partition coefficient of sulfate was not influenced by presence of
mNa2 SO4 ðvapÞ ammonia in the liquid phase. In this study forms of molecules such
KpNa2 SO4 ¼ (5)
mNaþ ðaqÞ mSO2 ðaqÞ g3ðNa2 SO4 Þ
2 as sodium sulfate (Na2SO4), sodium bisulfate (NaHSO4) and sulfuric
4 
acid (H2SO4), as well as ions SO2
4 and HSO4 were considered. These
mNaOHðvapÞ forms of sulfate are rooted in weak electrolyte properties that
KpNaOH ¼ (6)
mNaþ ðaqÞ mOH ðaqÞ g2ðNaHSO4 Þ

mNaHSO4 ðvapÞ
KpNaHSO4 ¼ (7)
mNaþ ðaqÞ mHSO4 ðaqÞ g2ðNaHSO4 Þ

mH2 SO4 ðvapÞ

KpH2 SO4 ¼ (8)
mHþ ðaqÞ mHSO2 ðaqÞ g2ðH2 SO4 Þ
4

where Kp is thermodynamic partition coefficient, m is concentra-

tion of compound or ion, mol/kg, g is mean stoichiometric activity
coefficient.
In order to determine the partition coefficients it was assumed
that the neutral molecules in vapor phase do not dissociate, in
liquid phase they are dissociated and the activity coefficient of
the neutral species in the vapor phase is unity. Further, obtained
dependence of thermodynamic partition coefficients on the
reciprocal temperature, as showed [29], proved that sulfuric acid is
the uppermost form of sulfate in the steam. Moreover, the content
of sodium sulfate in the steam is lower than sulfuric acid and higher
than sodium bisulfate. However, since the experiments were car-
ried out without the addition of other compounds in the liquid
phase it may be stated that obtained results can not be regarded as
sufficient for prediction the sulfate behavior in a thermal power
plant where chemical conditioning is applied. An additional
shortcoming was due to experimental equipment and measuring
procedure which were not wholly corresponded to the real pro-
cesses in drum boiler. Hereof, experimental study of behavior of
sulfate in water/steam cycle of power generating units, later con-
ducted at the Moscow Power Engineering Institute (Technical
University) [30], made allowance for conditions relevant to the
boiler water with all-volatile treatment which implies the addition Fig. 9. Concentration of sodium, chloride and sulfate in the feedwater: (a) EI, (b) CPO.
692 S. Vidojkovic et al. / Applied Thermal Engineering 59 (2013) 683e694

sodium sulfate exhibits at high parameters. Consequently, it is

subjected to hydrolysis according to the equations:

Na2 SO4 þ H2 O/NaHSO4 þ NaOH (9)

NaHSO4 þ H2 O/H2 SO4 þ NaOH (10)

Carry-over of sulfate is more complex than for chloride due to
divalent structure of sulfuric acid. Volatility of sulfuric acid makes
possible its transport to the steam. Acid form of sulfate is very
unfavorable for boiler tubes because it leads to the development of
acid corrosion, which results in an uniform removal of the pro-
tective layer and attack on the metal. Other sulfate compounds like
sulfur dioxide (SO2) and ammonium sulfate (NH4HSO4) can also be
carried in the steam by volatile carryover as discussed in the EPRI
guidelines [13].
Whereas various operating parameters and their interplays
produce an affect on the deposition process, the possibility of their
control is of particular interest to the reliable operation of power
plant. Experimental study, along with statistical analysis of vari-
ance (ANOVA), conducted by Peyghambarzadeh and Bahrami [31]
is one of the newest to allow the prediction of the contribution of
each investigated variable (heat flux, fluid velocity, concentration of
the solution, bulk temperature) to the deposition rate of sulfate
compound on the boiler tube surface and find optimal conditions
corresponding to its minimal content. The applied method gave
strong evidence of the least influence of velocity but also prevalent
effect of concentration which rapidly increases the deposition rate.
In similar experimental investigations Peyghambarzadeh et al. [32] Fig. 10. Concentration of iron and copper: (a) EI, (b) CPO.
came to a conclusion that bubble generation intensify deposition
formed by precipitation from the solution because of enhanced
supersaturation near the heat exchange surface and developed a of brass condenser and low pressure heater tubes made also from
model [33] for the prediction of deposition rate of calcium sulfate copper alloy. Copper deposit consists of oxides: Cu2O and CuO. In
on the basis of asymptotic type model. These models demonstrated some cases, copper can be found in form of crystals between layers
a perspective approach that could be enforced modifying deposit of magnetite. The corrosion process of copper parts in steam gen-
components and parameters relevant to typical power plant eration system is enforced by presence of oxygen and ammonia
conditions. what can be described by following equations:
Iron: in accordance with design specification of investigated
boiler, normal value for iron concentration in feedwater in actual 2Cu2 OðsÞ þ O2 ðgÞ ¼ 4CuOðsÞ (11)
TPP was maintained less than 20 ppb. The obtained values for
concentration of dissolved iron (Fig. 10) were in the range of 0.5e
5.5 ppb in EI and 4.2e16 ppb in CPO (Table 5) that can be regarded CuOðsÞþ4NHþ  2þ
4 ðaqÞþ2OH ðaqÞ ¼ CuðNH3 Þ4 ðaqÞþ3H2 O (12)
as normal. However, tendency in contemporary guidelines is to
lower values of iron in feedwater. Thus, target value in feedwater Copper compounds are transported through water/steam cycle
according to VGB [12] is below 10 ppb and to EPRI guidelines [13] reaching the turbine. Volatility carryover of dominant copper
below 2 ppb. The correct function of condenser polisher allows compounds in steam, cupric hydroxide (Cu(OH)2) and cuprous
removing iron from water/steam cycle to some extent and keeping hydroxide (CuOH), is very high over a broad range of temperatures
its concentration within permitted ranges. Also, very important and pressures that has a deleterious effect on high pressure turbine.
role in reducing iron concentration will have maintenance of stable Owing to protect copper constituents of power plant unit
pH value and possible implementation of automatic ammonia and minimize copper concentration in condensate and feedwater
dosing, then, reducing condenser leakage, and good deaeration. The system, oxygen should be minimized. In case of actual power
continuation of weekly and, in case of need, daily laboratory control plant it could be achieved by dosing hydrazine at the condensate
of iron content is indispensable measure for avoiding iron settling pump discharge and provide limited value of oxygen less than
on boiler tubes and transferring undesirable deposition throughout 10 ppb. Currently, hydrazine is fed on EI only. However, if oxygen
entire power chemistry cycle. decreasing is not feasible ammonia content has to be decreased and
Copper: the obtained values for copper (Fig. 10) were 1.5e12 ppb strict maintenance of ammonia concentration in feedwater should
in EI and 0.5e3.2 ppb in CPO (Table 5). Limit for copper level in be provided. On the basis of the EPRI guidelines [15] for copper in
feedwater is less than 3 ppb according to power plant technical fossil plant keeping reducing conditions (ORP at 300 to 350 mV)
specification. Measured concentration of copper was outside of in the area of passive Cu2O are regarded to be auspicious. Many
normal values but only a third analysis exhibits a fairly large de- power plants have solved problem with copper deposit by
viation which is four times above allowed value. Copper limits in replacement of low pressure heaters manufactured from copper-
feedwater amounts below 2ppb in Economizer Inlet based on EPRI alloy with new heaters from stainless steel. In actual plant data
guidelines [13]. According to VGB guidelines [12] 1imit for copper for previous three years, no evidence on copper measurements.
in feedwater is more strict and amounts bellow 1ppb. The primary Hereof, weekly laboratory control of copper in feedwater was
cause of copper presence in the deposit on the boiler is degradation suggested.
 S. Vidojkovic et al. / Applied Thermal Engineering 59 (2013) 683e694 693

TOC: performed analysis on content of organic matter Acknowledgements

showed that concentration of total organic carbon was not
exceeded normal value and amounted below 300 ppb (Table 5). This research was supported by the Ministry of Education, Sci-
Generally, makeup water is considered to be the major source of ence and Technological Development of the Republic of Serbia
TOC contamination entering the plant chemistry cycle under (Projects No. III 43009 and No. 45012).
normal condition, either from raw surface water or from
deionization resin deterioration. KEMA (Netherlands) conducted Nomenclature
research [34] in a real power plant using raw water source to
evaluate the behavior of organic compounds in the makeup AVT(R) reducing all-volatile treatment
water plant and observed that they are just partly removed in an BW boiler water
ion exchange resins. For that reason, monitoring of make-up CPD condensate pump discharge
water quality for total carbon content is recommended. CPO condensate polisher outlet
Several techniques for measurement of organic matter were DI deaerator inlet
developed so far and summarized by Maughan and Staudt [35]. DO deaerator outlet
It may be noted that all automated TOC analyzers are based on GF-AAS graphite furnace atomic absorption spectrometry
oxidation TOC to CO2 which is then measured and used to es- EI economizer inlet
timate the TOC concentration. So far, investigated power plant IC ion chromatography
has not enforced TOC monitoring. The limit of TOC in make up ISE ion selective electrode
water is determined in order to achieve the desired steam purity NDIR non-dispersive infrared
and this is the reason for variation of limiting concentration RS reheated steam
from low (15 ppb) to higher ranges (over 100 ppb) as demon- SS saturated steam
strated in the specific VGB guidelines [17] devoted to the organic TOC total organic carbon
matter behavior in the water/steam cycle of power plant. Ac- TPP thermal power plant
cording to the EPRI guidelines [13], recommended target value UV/VIS ultravioletevisible spectrophotometry
for make up water is less than 300 ppb. In an exhaustive WTPO water treatment plant outlet
overview of behavior of organic impurities in the power
chemistry cycle Svoboda et al. [16] highlighted their side effects
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