Impact of Boiler Water Chemistry On Waterside
Impact of Boiler Water Chemistry On Waterside
Impact of Boiler Water Chemistry On Waterside
EAUX CHAUDIERE
Mohammed Benfriha
Abstract
This paper emphasis on the study of typical premature failure of water wall tubes of two thermal power plant boiler of same
capacity (250 MW) and same operational parameter but with different boiler water chemistry. The investigation concludes on
the waterside corrosion in both of the case. One boiler is running with coordinated phosphate treatment (CPT) and another with
all volatile treatment (AVT). The causes of corrosion were discovered and proposed measures for their elimination were given.
Visual examination, chemical analysis of deposits, oxide scale thickness measurement and micro structural examination were
carried to ascertain the probable cause/causes of failure. From the investigation, it was finally concluded that the combination of
localized high tube metal temperature and wall thinning due to under deposit corrosion led to the premature tube failure in boiler
running with coordinated phosphate treatment and localized pitting corrosion in boiler running with AVT. Based on the results
and discussions, a possible way to combat the corrosion was proposed.
Keywords: Boiler Water Chemistry, Boiler Tube Failure, Caustic Gauging Corrosion, Pitting Corrosion, Boiler Deposits
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I. INTRODUCTION
Thermal power plants contribute about 75% to all India installed capacity of electric power generating stations. In worldwide
energy sector, about 37% of electricity is produced by combusting coal [1-2]. Most of the Indian industrial boilers has been a
prominent problem of boiler tube failure (BTF). The tube failure causes loss in generation and which in turn responsible for
massive economic loss. All type of boiler tubes have their defined life period and can fail due to various failure mechanisms. So,
Successful and reliable operation of steam generating equipment needs the use of the best available methods to prevent scale and
corrosion. In the boiler feed water cycle the ingress of contaminants, deposition of contaminants, and corrosion were found as the
major carriers of potential problems who may have major role for the analysis of boiler tube failures. Failure can occur in all
boiler areas: economizers, waterwalls, super-heaters (SH) and re-heaters (RH). Figure 1 shows simplified schematic of a coal
fired sub critical boiler. The boiler tubes are of various sizes and thickness depending upon the pressure and mid wall metal
temperature. According to the failures by location, water wall tubes are the second highest failure location after superheater
tubes. However, according to the failures by material, carbon steel tubes statistically lead as the most frequent material causing
failures. Correct tube material selection to resist the surrounding temperature is also one other decisive factor to stop the chances
of BTF. Normally the water touched areas like economizer and waterwalls are made of boiler grade carbon steel. Superheater
and reheater will have combination of low alloy tubes of stainless steels tubes. Figure 2[a] and [b] show the schematics of heat
transfer modes in the radiant and convective section of coal fired boiler. When the tube metal is in contact with the steam over
period of time, the oxidation process may begin to form a layer of protective magnetite (Fe 3O4) scale. Ferrous hydroxide [Fe
(OH) 2] is believed to be an intermediate in this process, converting to magnetite above 100°C according to the Schikorr reaction:
Fe + 2 H2O → Fe (OH) 2 + H2
Followed by reaction:
3Fe (OH) 2 → Fe3O4 + 2 H2O + H2
The resulting protective metal oxide acts as a barrier against further corrosion, which passivates the metal and inhibits further
oxidation. Corrosion in the boiler is prevented by maintaining a boiler water condition in such a way that the magnetite layer is
retained. Boiler water has to be at a pH of 9 to 10.2 in order to preserve the magnetite layer of steel. Iron oxidation in boilers
results in the formation of two magnetite layers. The outer layer is porous, is easily penetrated by water and aggressive ions, and
is the site of surface reactions. The inner layer is relatively less porous, and its growth is determined by diffusion of chemical
species through the layer. Numerous laboratory and field test results have shown that protective oxide layer adhere uniformly to
the surface along the height of boiler waterwalls and its associated components [1, 2]. It is marked from the work of many
researchers that the initiation of any of the corrosion mechanisms requires interruption of the protective oxide film formed on the
boiler interior surface and that often such disruption is the result of water treatment irregularities. In the extended contact this
phenomenon will worsen situation that leads to potential creep rupture problems. As corrosion and scale deposition are time-
dependent phenomenon, optimization of water chemistry is an important operational issue. In coordinated phosphate treatment,
boiler water conditioning is done by dosing tri sodium phosphate (TSP) in boiler drum through high pressure (HP) dosing
system, ammonia at condenser extraction pump (CEP) discharge and hydrazine at deaerator outlet. In all volatile treatment, this
is done by dosing only ammonia or various polyamines at condenser extraction pump (CEP) discharge and hydrazine at
deaerator outlet. The most popular water treatment scheme for sub-critical boilers is ammonia/hydrazine (AVT) feed water
treatment. Hence, the safe and corrosion-free operation of a boiler requires proper water monitoring and treatment, with
emphasis on the removal of possible corroding species [3, 4].
A critical analysis of the surface oxide film and corrosion products are capable of enlighten extensive information about the
mechanism of component degradation. On the occurrence of any power plant component failure, it is essential that the cause of
the problem be correctly recognized so that proper curative steps can be taken to avoid a recurrence. A flawed finding of a failure
can lead to improper corrective measures; which in turn gives the recurring problem. Usually, the problem area displays certain
explicit, noticeable signs. When these characteristics are properly interpreted, the cause of a problem and the remedy become
quite clear. The most common cause of corrosion are dissolved gases (primarly oxygen and carbon dioxide) in boiler feed water,
under deposit attack, low pH, and attack of areas weakend by mechanical stress and fatigue cracking. The table 1 shows the top
10 cause of failures statistically [4].
Table 1:
The top 10 cause of boiler tube failures
Failure causes Statistics
Creep(long-term overheating) 23.4%
Fatigue 13.9%
Ash corrosion 12.0%
Hydrogen damage 10.6%
Weld failures 9.0%
Short-term-over heating 8.8%
Erosion 6.5%
Oxygen pitting 5.6%
Caustic attack 3.5%
Stress corrosion attack 2.6%
Total 95.9%
and the temperature of the superheated steam are 540 °C. It used de-mineralized water as feed water. A co-ordinated phosphate
treatment was practiced in unit #1 of, while all volatile treatment (AVT) treatment is in practice in unit #2. The material
specification, design and operating parameters of the tubes as obtained from the plant along with failed tubes are shown in table
2 as follows:
Table 2:
Material specification, design and operating parameters of the failed tubes
Boiler Unit#1 Unit#2
Failure location water wall tube water wall tube
Tube material specification Carbon steel.st-20,Russia Carbon steel.st-20,Russia
Working temperature of the tube 380ºC 380ºC
Working pressure of the tube 158 kg/cm2 158 kg/cm2
Running hours 120,000 hrs (approx) 90,000 hrs (approx)
A. Visual Observations
Failed tube surface is ductile, thin edged and deposits near the site of attack are of dark brown colour due to formation of oxide
scale corrosion product deposits on the waterside of the tube. Fig. 3 shows the photograph of the failed tube samples. A
considerable signal of the localized wall thinning of the tube is observed. Thickness measurements show a severe reduction in
thickness from 4.25 mm (original thickness) to 0.8 mm.
C. Microstructural Observations
For the SEM observation of the damaged tubes of unit#1, specimens of tube were cut cross-sectional from the adjacent and apart
from the groove. The samples were then mounted and polished. After preparation, the samples were etched by nital 2% solution
for 15 seconds to explore the microstructure morphology of the sample. Observations of similarly sloping sections of an
undamaged tube having location absolutely opposite to the damage site of the affected tubes were made. In this way by
comparing the metallurgical observations between the various tube sections, a thought of the thermal condition of the damaged
section could be made. The scanning electron micrographs of samples were analyzed using SEM (MV2300 Cam Scan).
On examining across the tube wall at the damage location, decarburization near both the inner (Fig. 4) and outer surfaces of
the tube was observed, which is obvious from the diminished fraction of the pearlite grains near the tube surface. In contrast, the
sections taken from the unaffected tube showed no decarburization. Moreover, there was no pearlite lamellae dissociation (Fig.
5), nor any grain growth observed in the unattacked regions. A comparison of Fig. 4 with Fig. 5 brings out the microstructural
differences between the attacked and unattacked regions of the tubes. Fig. 6 shows the SEM cross sectional view of water side
deposit accumulated around the area of failure. The XRD results (Fig: 7) confirmed the presence NaFeO 2 which is the main
product of caustic corrosion. Therefore, it was concluded that the evaporation at the waterline of the partially filled tube leaded to
locally caustic concentration which dissolves the protective magnetite layer and consequently attacked the bare metal.
D. Result and Discussion of Root Cause and Mechanism of the Boiler Tube Failure
There are two main factors in incidence of caustic corrosion: (1) presence of caustics in boiler water and (2) concentration
mechanism. Load change is one of the main causes of phosphate hideout in which phosphate precipitates and consequently free
caustic may form. In order to control the water chemistry, giving continues blowdown or intermediate blow down is often
practised. But as the operating pressure does not change, this situation leaded to water/steam stratification and formation of
waterline in horizontal tubes. Above the waterline a high heat flux area formed and the water in contact with the tube wall at the
surface evaporated rapidly leaving behind contaminants. Under these conditions, dissolved solids such as NaOH or suspended
solids such as copper, iron began to concentrate. Simultaneously, phosphates accumulate in the concentrated liquid and
precipitated or reacted with surface scales. Then the locally concentrated NaOH at the waterline attacked the protective oxide
layer and bare metal. The protective iron oxide coating which is formed on the inner surface of the tube is an amphoter
compound and it is susceptible to be attacked by sodium hydroxide. At temperatures above 90 oC, the concentrated NaOH
attacks into the protective magnetite film by the following reaction:
2NaOH + Fe Na2FeO2 + H2
........ (3)
........ (4)
As a result of Eq. (2) – (4), Corrosion of base metal is taken place by gouging. In caustic solution, hydrogen produced by
dissolving the bare metal move to the solution instead of penetrating to the base metal. After elimination of the protective film,
the caustic solution enters the oxide layer. The trapped solution evaporates and consequently, pH beneath the oxide layer
increases. The presence of Cu in the deposit attributed to the impurity present in the feed water.
A. Visual Inspection
The figure no .8 depicts the typical failure of boiler end tubes of unit no.2 running with all volatile treatment (AVT). Failed tubes
ends shows groove and crack failure features immediately adjacent to the wide band where the tube had been rolled into the tube
sheet. On each tube the groove was approximately 1.5-inches long. These groove appeared to be the result of corrosion, mainly
due to its irregular surface. It was noted that the some tubes shows red, rusty appearance and some tubes black, shiny
appearance. Closer examination of a rusty tube revealed the presence of significant pitting, accompanied by rust-colored mounds
along its length (Figure: 9).
C. Microstructural Observations
One of the failed tube ends was sectioned longitudinally through the groove and crack for metallographic examination. Figure
10, shows the microstructure of undamaged tube just opposite to the location of failure. Figure 11 shows the microstrual view of
damaged tube. By comparing the differences between these two figures it is clear that the lack of deformation in the
microstructure of the failed tube has been occurred which confirms the corrosion as the cause of the grooving. The
microstructure consists of pearlite in an equiaxed ferrite matrix, typical of low carbon steel. It is also clear from the figure 10 that
there were no indications of overheating of the tube.
D. Result and Discussion of Root Cause and Mechanism of the Boiler Tube Failure
The boiler tube failures were caused by oxygen corrosion of the tubes produced by high level of dissolved oxygen in the boiler
water. The overview of boiler water chemistry parameter maintained in both boilers are depicted in the table no [4]. It is clear
that unit#2 was continuously running in the high value of dissolved oxygen. This may be due to the improper dosing of oxygen
scavenger „hydrazine‟ or may be due to the air ingress from vent line the condenser extraction pump or air leakage from
condenser sealing. On the basis of the rusty appearance of most of the failed tubes, the presence of pits and tubercles (typical
oxygen corrosion features) along the lengths of some of the failed tubes. Oxygen corrosion of the tubes at the failure locations
led to the grooving. The groove reduced the tube wall thickness and subsequently acted as a stress-raiser during normal thermal
cycling of the boiler. Stresses from thermal cycling eventually produced the final failure of the tubes by cracking. Under normal
(ideal) operating conditions boiler water is deaerated (i.e., less than 5 ppb). Under such conditions, low residual oxygen produces
a layer of black iron oxide (magnetite), which protects steel tubing. Thermal cycling can fracture the magnetite layer, which
exposes underlying bare steel to the boiler water. In the presence of excessive dissolved oxygen in the boiler water, accelerated
corrosion of the steel tubes occurs.
VI. CONCLUSION
The failure of boiler tubes in unit#1 practising coordinated phosphate treatment concluded to have problem of caustic gouging,
as the presence of distinct hemispherical or elliptical depressions on the inside surface of the tube filled with a thick layered
deposits, containing crystals of sodium ferroate. Final failure will be caused by progressive wall thinning leading to a thin Edged
fracture in a region of reduced wall thickness. Hence possibility of caustic attack is confirmed. As in the coordinated phosphate
treatment the chances of excess formation of NaOH due to over dosing of TSP is common phenomenon especially during start-
ups. Unit #2 with AVT boiler water treatment shows typical features of pitting corrosion as evidenced by the presence of pits and
tubercles along the length of failed tubes. It is also concluded that unit is under dosing of hydrazine. The unit have to increase the
dosing of hydrazine to combat such type of corrosion especially during preservation of boiler.
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Fig.2 (a): Heat transfer in the radiant section Fig. 2 (b): Heat transfer in the convection section
Fig. 3: Failed boiler tube samples collected from UNIT#1 Fig. 4: Caustic Corrosion in waterwall tube
Fig. 5: Normal pearlite and ferrite structure in unaffected tube Fig. 6: SEM View of Deposit Cross Section
Fig. 8: Pits and tubercles observed on failed boiler of failure: groove and crack
Fig. 11: Microstructure of failed tube showing pearlite in ferrite matrix (125X Original Magnification)
Table 3:
Chemical analysis of the failed boiler tube (Unit#1)
Component (Wt %) C Si P Mn S Cr Ni Mo Fe
Unit #1 0.15 0.19 0.015 0.52 0.004 0.03 0.02 0.02 99.05
Table 4:
Chemical analysis of the failed boiler tube (Unit#2)
Component Wt %) C Si P Mn S Cr Ni Mo Fe
Unit #2 0.14 0.19 0.016 0.54 0.004 0.03 0.02 0.02 99.12
Table 5:
Deposit analysis of the failed boiler tubes after 40000 hrs of the operation
Component (Wt %) Fe203 SiO2 CaO MgO Al2O3 P2O5 CuO
Case 1 84.20 3.22 1.48 0.98 0.65 5.30 2.21
Case 2 80.10 2.20 3.45 1.96 0.54 1.30 0.46
Table 6:
Various boiler water parameters at the various locations of boiler of Unit #1
Deminerlized Condensate Feed Boiler drum Main steam
Parameters units
water sample Water sample Water sample sample sample
pH 6.9 8.9 8.9 9.2 9.0
Electrical Conductivity µs/cm 0.06 5.82 5.56 18.54 5.60
Silica ppm 0.018 0.02 0.022 0.20 0.02
Phosphate at drum ppm - - - 4.0 -
Residual hydrazine ppb - - 20 - -
Residual
ppm - 0.5 - - -
ammonia
Dissolved oxygen ppb - 30 7 - -
chloride ppm - 0.01 - - -
Iron ppb - - 10 10 10
Copper ppb - - 6 6 6
Sodium ppm - - - 0.3 0.3
Table 7:
Various boiler water parameters at the various locations of boiler of Unit #2
Parameters units Deminerlized Condensate Feed Boiler drum Main steam
water sample Water sample Water sample sample sample
pH 7.0 8.9 8.9 9.1 9.0
Electrical µs/cm 0.06 5.82 5.56 8.91 5.60
Conductivity
Silica ppm 0.018 0.02 0.022 0.20 0.02
Residual ppb - - 15 - -
hydrazine
Residual ppm - 0.6 - - -
ammonia
Dissolved ppb - 40 10 - -
oxygen
chloride ppm - 0.01 - - -
Iron ppb - - 8 9 8
Copper ppb - - 5 5 5
Sodium ppm - - - 0.1 0.1