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Deterioration of economizer tube in utility boiler

Chidambaram Subramanian

PII: S1350-6307(19)31373-1
DOI: https://doi.org/10.1016/j.engfailanal.2020.104643
Reference: EFA 104643

To appear in: Engineering Failure Analysis

Received Date: 16 September 2019

Revised Date: 2 May 2020
Accepted Date: 31 May 2020

Please cite this article as: Subramanian, C., Deterioration of economizer tube in utility boiler, Engineering
Failure Analysis (2020), doi: https://doi.org/10.1016/j.engfailanal.2020.104643

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 Deterioration of economizer tube in utility boiler
Chidambaram Subramanian
NDT & Metallurgy Group, Central Mechanical Engineering Research Institute-CSIR, M.G. Avenue, Durgapur-713209, West Bengal, India
chidambaram@cmeri.res.in
ARTICLE INFO ABSTRACT
Keywords: Steam generation from intermediate petroleum products of different hydrocarbon
Economizer tube processes ensures zero waste in oil and gas industries. The generated steam is again used
Acid dew point for production of refinery final products. Although, zero waste increases refinery margin,
Condensation there is downside associated with tube failure in utility boiler. Fire side corrosion occurred
Failure Analysis on economizer tube and failure was systematically analysed. A series of characterization
techniques were conducted to find out root cause of failure. Visual inspection, mechanical
characterization, plant data collection, morphology investigation of scales using SEM,
elemental analysis using EDX, and microstructural analysis were employed. Sulfur
content was precisely determined on fire side scale deposits. Steam side feed water and
steam products were analysed as well. Characterization of fire side deposits revealed iron
oxide scales with severe sulfur concentration as well. The results revealed that failure was
primarily owing to acid dew point corrosion and sulfur came from intermediate fuel oil
(IFO). The failure mechanisms were discussed and good engineering practices were put
forward to combat and mitigate acid dew point corrosion.
1. Introduction
Gas turbine is utilized for power production and waste heat from gas turbine system is used for steam generation in waste heat recovery
boilers. Generation of power primarily along with steam is referred as cogeneration system. Utility boiler is a kind of direct fuel firing boiler for
steam generation without power generation. The availability of steam to process units is paramount important in petroleum refinery for production
of various petroleum products. Therefore, utility boiler shut down will directly impact in downstream process units of a refinery plant [1]. One such
important case where the boiler was forced to shut down due to leakage is discussed in this paper. Fuel is directly fired in utility boiler for super
saturated steam generation. Numerous literatures are available to identify and prevent various kinds of failures in boiler tubes [2-6]. Accident and
disaster are persisting due to poor engineering practices. Various causes of failure reported in boiler tubes are stress corrosion cracking [2], high
temperature creep [3-5], graphite phase formation and erosion corrosion [6]. In addition to metallurgical failures, an oxygen entrapment in feed
water is frequently reported as a major cause of failure high pressure tubes and piping. Water side corrosion was reported as internal corrosion
accompanied with various deposit formation leading to under deposit corrosion [7]. During maintenance feed pump, boiler section and steam drum
are in open condition enables oxygen pick up from environment. Therefore, continuous treatment of boiler feed water by adding corrosion inhibitors,
neutralizers and scavengers to dissolve suspended organic, inorganic substances and removal of oxygen, nitrogen and carbon-di-oxide is essential.
In certain cases, it is reported that idle conditions of boiler are more prone to corrosion compare to normal operating conditions.
Early detection to prevent failures is limited [8]. Fire side corrosion and oxidation of boiler tubes are reported in literatures [9-21]. The
fire side corrosion occurs by interaction of SO3 or H2S or H2SO4 with typical construction material like carbon steel. Besides corrosion, the corrosive
products like ferrous sulfide will undergo spontaneous combustion in presence of air, which leads to fire accident in floating roof tank [22]. Flue
gas containing SO2 have result in sulfidation beneath oxidation on fire side of superheater tube [23]. The presence of H2S in gas well leads to
galvanic corrosion on carbon steel coupled with 17-4PH stainless steel as reported by Zhang et al [24]. Generally nickel alloys exhibit excellent
resistance in many sulfur containing environments, but Alloy 20 (ASTM B473 UNS N08020) was failed by erosion corrosion in sulfuric acid
medium [25]. The presence of corrosive sulfur in insulating oil can form copper sulfide which reduces the dielectric strength resulting to transformer
failure. Ricardo et al [26] demonstrated the prevention of power and transformer failures from corrosive sulfur. Besides chemical response of
various material in sulfur containing environment, the material composition containing sulfur impurities can also be suspected for pitting corrosion.
Tavares et al [27] has demonstrated that high sulfur content (0.027wt %) in 17-4PH steel revealed lower pitting resistance. Various researchers
suggest that sulfur is detrimental to materials which lead to destruction of equipments [9-27].
Table1 Utility boiler operating parameters
Parameters Unit Value collected from plant
BFW
Pressure ksi 60-65
Temperature ˚C 105
Operating flow rate ton/hour 30-40
Steam
Pressure ksi 38-40
Temperature ˚C 450
Operating flow rate ton/hour 30-40
Design flow rate ton/hour 53
Flue gas
Temperature in economizer inlet ˚C 340-360
Temperature in economizer outlet ˚C 140-150
Excess air % 20-30
Excess oxygen % 3-4
Furnace pressure mmWC 20-80
Forced draft fan pressure mmWC 200-300
Stack
𝑆𝑂𝑋 (Normal and max) ppm 7 and 20
𝑁𝑂𝑋 (Normal and max) ppm 9 and 50
CO (normal and max) ppm 1 and 30
 The economizer in current study has been operated in accordance with stringent design requirements. The economizer tube was failed and company
considered water side corrosion (internal corrosion) as a cause of failure which was questionable. In the present work, the sulfur content in
intermediate fuel oil attributed to acid dew point corrosion on fire side of the tube and practical recommendations were put forward to implement
as well.

2. Background information on operating conditions of boiler

The flue gas transfers heat to boiler tubes to produce super saturated steam and flue gas is generated by combustion of intermediate fuel
oil (IFO). The utility boiler operating parameters are shown in table 1. The fuel pipe is connected with four burners for continuous fuel supply and
average flow rate is in range of 8 l.min-1to11 l.min-1. The chemical constituent of fuel is shown in table 2. The de-mineralized (DM) water is
chemically mixed with volatile polyamine based chemicals for chemical dosing to convert DM water to BFW. 3kg of neutralizing amine is mixed
with 600L of DM tank and 3kg of cyclohexyl amine is mixed in operated boiler feed pump for every 4hrs. The metallurgy of economizer tubes are
BS 3059 Part 1HFS 320 carbon steel of outside diameter, 38.1 mm, thickness, 3.66 mm and maximum design temperature is 292˚C. The chemical
composition and mechanical properties of boiler grade steel specification is shown in table 3&4 [28]. The maximum allowable working pressure
(MAWP) and hydraulic test pressure of utility boiler is 50kgcm-2 and 75kgcm-2 respectively. The design pressure is specified as MAWP. The outlet
steam pressure and temperature are 42kgcm-2 and 456 ± 5˚C, respectively, and saturated steam temperature is 264˚C. BFW is treated in spray type
horizontal de-aerator to preheat 105˚C of a saturation temperature while rising steam is supplied by sparger from bottom to remove the dissolved
oxygen and carbon-di-oxide in feed water. The dissolved gases in feed water escapes through rising steam and vented to atmosphere. Few ppm of
hydrazine 𝑁2𝐻4is added to feed water for complete removal of oxygen. The total heating surface area for economizer and super heater coil is 1360.1
m2 and 291.4 m2 respectively. The failure location is shown in figure 1&2. The boiler was in service for past 21 years and fuel additives in fire side
treatment were adopted earlier.

Table 2 Chemical constituents and density of fuel

Fuel physical parameter and chemical constituents Unit Value collected from plant

Nickel ppm 21.6

Vanadium ppm 17.7
Sulfur wt% 0.58
Moisture ppm 0.78
Hydrocarbon (C20) wt% balance
Density at 15˚C g/ml 0.9641
.

Failure location

Duct
Stack

Water wall

IFO

Water wall

Figure 1 Schematic side view of utility boiler and dew point locations were encircled.
3. Experimental methods
The failed location of the boiler is visually inspected and selected samples were taken from tube without affecting the damaged portion
by cold cutting. Thereafter, the samples were photo documented and reviewed for past history. Fire side deposits are tested by infrared carbon/sulfur
analyser. The sample from unaffected area adjacent to failed tube was carefully chosen to evaluate the mechanical properties of boiler tube. Instron
universal tensile testing machine is employed to measure the actual material properties at strain rate of 10-3s-1. The hardness of the sample was
measured using diamond pyramid intender of MIC 201A model supplied by general electric. The chemical composition of the failed samples and
adjacent un-failed tubes were measured by x-ray fluorescence technique (XRF) using X-Met 7500 model supplied by oxford instrumentation. As
received tube samples were examined for micro morphological investigation on both water side and fire side. Elemental analysis was also conducted
on 2𝑐𝑚 × 2𝑐𝑚 × 2𝑐𝑚 (𝑙 × 𝑤 × 𝑡) prepared samples from water side and fire side of the failed tube. The morphological studies were conducted
using scanning electron microscope Vega L2 model and elemental analysis conducted using energy dispersive X-ray spectroscopy attached in SEM.
The metallography samples were prepared from both fire side and water side of failed tube using standard metallographic techniques to get mirror
 like scratch free surface appearance of 0.25µ finish and etched in 2% nital solution. The samples for SEM/EDX and metallography were selected
within the marked circle as shown in figure 3b.BFW samples are subjected to water analysis and produced steam samples are subjected to physical
and chemical analysis.

4. Investigation results

4.1. Visual observations

Visual examination was conducted on economizer tube banks and leakage was detected in one tube of straight bank. In addition series
of elbows were thoroughly inspected to identify any leakages and no leak was observed other than one tube. An overall economizer tube surface
was in wet condition during dry inspection. A perforated hole was detected on leaked tube located close to peephole door (refer figure 2 & figure
3). The internal side of the tube appears to have brownish layer with scale deposits (refer figure 4a) and external surface appears to be affected by
non-uniform corrosion (refer figure 3b). Adjacent to perforation appears to be ridges with shallow dents. The actual tube metal temperature of the
failed tube was measured by attached thermocouple. The average temperature of 7100 boiler operating hours (excluding start up and shut down)
prior to occurrence of failure was found to be 140° close to the failure position of the tube. The random elbow from economizer bank was sectioned
for visual inspection and no significant damages were observed (refer figure 4b). Figure 5a shows schematic of perforate hole position indicated by
arrow located intermediate between front side of vertical tube and peephole side wall from boiler front face (adjacent to front side from direction
of tube bundle). Figure 5b shows that perforate hole (indicated by arrow) located at an approximate angle 60° to the vertical tube axis. The chemical
composition was measured using positive material identification and shown in table 3. Adjacent series of elbows and tubes were randomly measured
for its chemical composition and it shows similar chemical composition as shown in table 3. From chemical testing the metallurgy of economizer
bank of tubes was found to be carbon steel as specified in design drawing. After removing wall panels, wall thickness was measured in the area
adjacent to failure using ultrasonic thickness gauging and minimum thickness was 1.1mm. The wall thickness of investigated tube at various marked
locations (refer figure 3a & 5b) is shown in table 4.

Table 3 Chemical composition of failed tube measured by XRF technique

Elements in weight percentage (%) C Mn P S Si Fe

Specification [28] 0.16max 0.30 – 0.70 0.050max 0.050max ---- balance

Failed economizer tube ---- 0.55±0.02 0.02±0.01 0.02±0.01 0.03±0.01 balance

70 x 29 = 2030 70 x 29 = 2030

Economizer top header

Economizer bare tubes

Leakage

Peephole door
Peephole door

Economizer bottom header

Figure 2 Economizer coil assembly of boiler (front view) having 58 vertical tubes in first row. Seventy similar rows were assembled of total 4060
tubes in economizer bank
 a) 4
b)
Perforate hole
Light
7 3

6
6
8
1 5

Perforate hole

Figure 3 Failed tube a) view from water side, b) view from fire side after slight removal of deposits.

a) b)
Adjacent elbow
without leak
Internal scale
Internal scale

Figure 4a) Uniform scale formation on adjacent to failure and b) elbow connected to economizer bank shows no failure.
0°
1
3 1

6 5 6
7
4
270° 90°
2
Rear side

Front side

8
a) 180° b)

Figure 5a) Schematic of economizer tube with perforate hole at location 6 and b) perforate hole located at an approximate angle of 60° to the tube
axis clockwise. Thickness location1 facing burner side while location 2 & 4 were facing towards peephole sidewall.
Table 4 Thickness of the investigated tube
Location 1 2 3 4 5 6 7 8
Thickness, mm 2.7 3.0 3.0 2.7 1.2 1.1 1.2 3.0

4.2. Past inspection records

This boiler underwent annual shutdown every year and several unplanned shut downs owing to several failures such as tube leak in
super heater, weld failure in economizer tube, tube bulge in evaporator and corrosion (pinhole) failures in steam drain line close to economizer
section. No reduction in tube wall thickness was reported for economizer bank. No hydro jetting operation was employed to clean external tube
surfaces for past three years.

4.3. Mechanical characterization

The mechanical property of the tube adjacent to failed location is shown in below table 5. It is observed that maximum yield strength,
maximum tensile strength and elongation was above the minimum value as specified in boiler design codes and standards. The hardness of the
 failed tube was measured and these values are shown in table 5 confirms that material hardness is within the limit. The mechanical properties of
failed economizer tubes were evaluated and deviations were not observed.

Table 5 Mechanical properties of failed tube

Mechanical properties Yield strength Tensile strength Elongation Hardness

Specification [28] 195 MPa min 325 – 480 MPa 22 187 BHN
Failed economizer tube 210 MPa 415 MPa 22 165 BHN

4.4. As received condition of samples

As received specimens are in wet condition and further dried in oven to remove the moisture. Both fire side and water side surface were
examined for micro morphological features. As received fire side deposits appears to be black (Fe3O4) and investigation was conducted in field
samples after drying at 75°C. Micro morphological investigation confirmed that iron oxide scale was formed on boiler tube water side and fire side
surfaces. The passive layer formation on water side from BFW predominantly constitutes magnetite that retards water side corrosion (refer figure
6a&b). The silica particle evidence on fire side led to grooving and increases fire side corrosion rate on grooved marks (refer figure 7a-b and 7g).
Approximately 35µ silica particle erodes the fire side surface and might increases corrosion rate faster to result in leakage. Similar results have also
been observed by other researchers for carbon steel [10, 18]. Moisture is present in fire side boiler environment and passing flue gas induces tensile
stress in oxide scale due to pressure built. It will lead to an oxide scale crack appears to be brittle cleavage and sulfur compound can penetrate
through the crack (refer figure 7c&d). Once an oxide crack is initiated and further propagated, it is difficult to prevent the penetration of sulfur ions
in to metal surface. Fire side deposit perforation appears to be hole and unprotective (refer figure 7e). Furthermore, flue gases push sulfur deep into
crack and hole (un-protective) by an operating pressure. Flower like scale deposits are characteristics feature of magnetite𝐹𝑒3𝑂4 due corrosion
reaction (refer figure 7f) and similar results were also reported [9, 13].

a) b)

Figure 6 a) SEM image of water side surface deposits, b) partial amplified view of figure a shows passive layer.
 a) b)
Silica particle

Spectrum 3

c) d) Crack

e) f)

Figure continued and figure caption at next page

 g
Element Weight% Atomic%

Si K 0.51 1.00
Fe K 99.49 99.00

Totals 100.00 100.00

Figure 7 SEM image of a) topography of agglomerated deposits, b) hexagonal silica particle, c) & d) crack formation, e) perforated hole in scale deposits
shown by arrow, f) iron oxide scale and g) EDX spectrum3 shown in figure b, on fire side of tube.
4.5. Elemental characterization
Fire side and water side surfaces of the failed tube were examined using EDX to analyse the various elements present on both sides of
tube. The fire side reveals localized grooving and corrosion as shown in electron image (refer figure 8a). Corresponding elemental analysis reveals
significant concentration of sulfur ions on external surface of the tube (refer table 6). The source of sulfur was derived from flue gas and sulfur in
flue gas forms𝑆𝑂2, sulfur-di-oxide and𝑆𝑂3, sulfur-tri-oxide in economizer zone. Significant concentration of silica particles were detected on the
fire side and source of silica might have arrived from the dust particles settled in fire side boiler environment. The source of silica also arrived from
flue gases and abrasive silica particles (𝑆𝑖𝑂2) probably derived from fly ash [9]. It is inferred that abrasive particles can remove the metal appears
to be grooves on fire side surface. Similar result was obtained by Alireza Bahadori et al and he demonstrated that the size of silica particles ranges
from 100µ to 500µ [18]. It is suspected that silica particles affect superheater, evaporator and economizer tube sequentially along the flue gas path.
On fire side tube surface significant concentrations of copper ions attributed to fuel additives of fire side treatment. Also brass wire brush used after
welding for slag removal during construction or repair might also been suspected source of copper. “Sour crude” is raw material for crude oil and
vacuum residue is obtained from distillation of crude oil. Furthermore, vacuum residue is heated at 360°C in presence of catalyst to produce
intermediate fuel oil (IFO). It is inferred that fuel oil is contaminated due to poor quality of raw crude and Cr, Zn, Al, & Ti ions present in scales
are attributed to fuel oil contamination by catalyst. The boiler was subjected to hydraulic test annually as a part of statutory inspection. The treated
water was utilized for such hydraulic test for leak detection. During such tests the treated water probably settled inside the boiler due to improper
draining. On cold start the calcium ions in treated water might deposited on fire side of the tube. Contrastingly, water side of the tube contained
iron and manganese ions with oxide scales (refer figure 8b).

a)

b)

Figure 8 SEM image and corresponding elemental analysis from a) fire side and b) water side of failed tube.
 Table 6 Elemental analysis on fire side and water side of the economizer tube
Elements Spectrum 1 Spectrum 2
Weight % Atomic % Weight % Atomic %
OK 10.53 28.92 24.59 53.23
Mn K 0.33 0.26 0.13 0.08
Fe K 81.32 63.95 75.28 46.69
Al K 0.32 0.53 --- ---
Si K 0.57 0.90 --- ---
SK 0.69 0.94 --- ---
Ca K 0.23 0.25 --- ---
Ti K 0.17 0.16 --- ---
Cr K 0.45 0.38 --- ---
Cu K 5.06 3.50 --- ---
Zn K 0.33 0.21 --- ---
Total 100 100 100 100

4.6. Analysis of fire side deposits

Fire side deposit on failed sample was tested using infrared carbon/sulfur analyser. Five more fire side deposit samples were randomly
collected from economizer bank to determine sulfur content. Sulfur was detected in all samples (refer table 7) and sulfur constituent in failed sample
is higher (0.185 wt %) than remaining (random) samples. It is validated that sulfur to be exist on fire side deposits. However, by comparing EDX
results (table 6) with infrared carbon/sulfur results (table 7) sulfur was predominantly higher (0.69 wt %) in former than latter ones. EDX measures
localized corrosion product scale which has higher concentration of sulfur but carbon/sulfur analyser measures average content of large size
mixtures removed from fire side deposits.

Table 7 Sulfur content of fire side deposits

Constituent (wt %) Sample1 Sample2 Sample3 Sample4 Sample5 Sample6

Sulfur 0.185 0.114 0.099 0.065 0.103 0.111

4.7. Metallographic investigation

The fire side of the failed tube adjacent to failure reveals corrosion in un-etched condition as shown in figure9. The metallographic structure
of failed economizer tube reveals ferrite and pearlite phases (refer figure 10a-d). The white phases are ferrite and dark phases are pearlite, which is
elongated in principle working direction. The tube reveals ferrite pearlite inter-phase boundaries and shows deformation characteristics across the
microstructure. The corroded perforated hole observed in fire side of tube (refer figure 10a). The pearlite phase is corroded along its oriented
direction and attacked by sulfur present in flue gas that forming sulfur compounds from fire side. The moisture within boiler environment chemically
reacts with sulfur in flue gas to form sulfur-di-oxide, sulfur-tri-oxide and sulfuric acid on fire side and condense at temperature below 150°C. The
condensed water on the metal surfaces saturated with oxygen lead to external corrosion. The corroded oriented pearlite appears as directional
corrosion pattern as shown in figure 10b. Owing to manufacturing (hot rolling) preferred orientation was existed in tube and sulfur compound
corrode oriented pearlitic structure. Both ferrite and pearlite has been corroded depending upon localized chemical reactivity with sulfur compound,
condensation location and dilute weak acid environment. The concentration and diffusion of sulfur compound especially SO3 is responsible for
deterioration of microstructure below acid dew point. The transverse tube section adjacent to failure shows few pearlite were attacked and it might
actively involved in perforation of the wall thickness (refer figure 10c). Both ferrite and pearlite phases were undergone corrosion on fire side but
no corrosion was noted on water side of the tube (refer figure 10d). The quality of boiler feed water and magnetite passive layer formation on water
side might be avoiding water side corrosion (internal corrosion). The visual appearance during initial stage of inspection (refer figure 4a) reveals
uniform magnetite layer which predominantly prevented the water side corrosion. The microstructure can resist water side corrosion after reducing
oxygen scavengers by chemical dosing techniques.

Figure 9 Microstructure of failed tube adjacent to failure on fire side in un-etched state. Light microscopy.
 a) b)

Corrosion

100µm

50µm

c) d)

50µm 50µm
Figure 10 Microstructure of: a) failed tube on fire side, b) close to failure zone, c) transverse section and d) water side, of tube near failure in etched state. Light microscopy.

4.8. Boiler feed water (BFW) and steam analysis

BFW samples were collected sequentially from BFW drum and cold blow down (CBD) system, and water analysis conducted once in
day for past 1 year and average of 320 test results before failure is reported (7750 boiler operating hours excluding downtime). Similarly saturated
and super saturated steams were collected from superheater section (sample collection point) for similar analysis. The physical and chemical
properties of feed water and steam were measured [7, 29] and tabulated in table 8. The pH of feed water, CBD and steam is 8.5. The dissolved
oxygen in boiler feed water is measured to be very low as 2.5 ppb and it is absent in CBD and produced steam. The oxygen content in the BFW
was removed by de-aerator process and hence dissolved oxygen in steam was avoided. The conductivity of BFW and CBD were 24.7ohm.cm-1 and
32.1ohm.cm-1 respectively and conductivity was continuously maintained less than 100ohm.cm-1 (set limit). The total dissolved salt (TDS) of BFW
and CBD were measured to be 25.94ppm and 28.89ppm respectively and TDS was continuously maintained less than 100ppm (set limit). The
phosphate content in BFW was measured to be 12ppm but nil in remaining tested samples. The BFW was operated within plant set limits by
deactivating corrosive species in feed water to produce good quality steam generation.

Table 8 Average test results of boiler internal fluids

Measured parameters Unit BFW CBD Saturated steam Superheated steam
pH ---- 8.5 8.5 8.5 8.5
Dissolved oxygen ppb 2.5 ---- ---- ----
Conductivity ohm.cm-1 24.79 32.16 ---- ----
TDS ppm 25.94 28.89 ---- ----
Phosphate ppm 12 ---- ---- ----

5. Discussions
Economizer bank was wet and failure occurred during night (low humid) hours. As pH of BFW in present study is 8.5 (table 8) and
potential of carbon steel is -0.44volts, magnetite (Fe3O4) can act as passive layer in water side of boiler service, which prevents steel against water
side corrosion [30]. Considering that absence of corrosive species in BFW and no evidence of corrosion from water side microstructure, the
possibility of water side (internal) corrosion is ruled out. The combustion of fuel (IFO) is oxidizing in nature and presence of sulfur in fuel perforate
the carbon steel by fire side corrosion. An operating temperature is critical factor in determining the rate and severity of corrosion damage.
The moisture entrained into boiler can produce corrosion product scales as stated in equation 1-4. The formation of corrosion scales
such as magnetite𝐹𝑒3𝑂4, ferric oxide𝐹𝑒2𝑂3 and ferrous oxide 𝐹𝑒𝑂 strongly depends upon oxygen concentration and temperature available in
economizer. The sulfur in IFO oxidized to SO2 according to equation 5. The formation of SO3 is favored in presence of vanadium or other metals
beyond 400°C according to equation 6, which is a reversible reaction. After that, sulfur trioxide reacts with available moisture to form sulfuric acid
below dew point and it is called “acid dew point” as stated in equation 7. The localized chemical reaction is controlled by diffusion of sulfur
compounds that evolves from flue gases lead to dissolution of microstructure below 150°C. The condensation of sulfur species forms sulfuric acid
below dew point. Subsequently it will react with steel and iron oxides to form iron sulfate as shown in equation 8 & 9.

3𝐹𝑒 + 4𝐻2𝑂→ 𝐹𝑒3𝑂4 + 4𝐻2 (1)

3𝐹𝑒 + 2𝑂2→ 𝐹𝑒3𝑂4 (2)

4𝐹𝑒 + 3𝑂2→ 2𝐹𝑒2𝑂3 (3)

2𝐹𝑒 + 𝑂2→2FeO (4)

𝑆 + 𝑂2→𝑆𝑂2 (5)
1
𝑆𝑂2 + 2𝑂2→ 𝑆𝑂3 (6)

𝑆𝑂3 + 𝐻2𝑂→ 𝐻2𝑆𝑂4 (7)

𝐹𝑒 + 𝐻2𝑆𝑂4→𝐹𝑒𝑆𝑂4 + 𝐻2 (8)

𝐹𝑒 + 𝐹𝑒3𝑂4 +4𝐻2𝑆𝑂4→ 4𝐹𝑒𝑆𝑂4 + 4𝐻2𝑂 (9)

Referring to previous literatures [21, 31], it is known that dew point temperature can be varied by concentration of both SO3 and moisture
in flue gas. On one hand, for fixed SO3 concentration, an increase in moisture content can increase acid dew point temperature whereas on other
hand, for fixed moisture content, even small increase in SO3 concentration especially between 0.1ppm to 100ppm will also increase acid dew point
temperature [31]. Generally, boilers in oil refineries opt for air firing when compared to other process such as oxy fuel firing. The combustion using
oxy fuel firing will lead towards higher concentration of SO3, which attributes to increase in acid dew point temperature. During oxy fuel
combustion, an increase in CO2 formation will enhance secondary formation of SO3 [21]. Similarly, oxidizers in oxy fuel will also increase SO3
concentration [21]. Therefore, conversion of sulfur during combustion affects the dew point temperature. Air firing lowers SO3 in flue gas when
compared to oxy fuel firing. This utility boiler was air fired and air was drawn from blower as shown in figure 13.
The tube metal temperature varies depend upon entry temperature of BFW (TBFW = 105°C) and exit temperature of flue gas (TFG=
140°C), and if both the temperatures were lower than operating limit will lead to external corrosion. The sulfuric acid attacks external un-protective
magnetite layer (refer figure 7c&e) through which corrosion progresses and flowing flue gas pushes an acidic mist onto tube surface. The sulfuric
acid attacks both ferrite and pearlite (refer figure 10a&b) depend upon localized location of condensation. Below dew point temperature the
corrosion rate is depend upon condensation of individual species, extent of protective corrosion products, soot and ash deposition. The soot and ash
deposit can act as a chemical barrier for acid gas as similar thermal barrier between environment and tube. However, weak dilute acid react with
deposits to deteriorate bare tube.

Current study
Figure 11 Sulfur wt% vs. dew point temperature plot [32]
The moisture in flue gas at acid dew point temperature reduces oxygen at salt metal interfaces form sulfur precipitation. Concurrent
precipitation of sulfur will occur on fire side of tube close to peephole door (refer figure 2). The ferrite and pearlite phase are less immune to acid
dew point especially in dilute week acid environments. Once the tube perforate water jet impinges erodes adjacent tubes at faster rate and available
moisture significantly increases corrosion rate of nearby tubes. The formation of 𝑆𝑂2on bare tube surface is stable in normal humid conditions but
conversion of 𝑆𝑂2to 𝑆𝑂3will occur only if excess oxygen prevails in environment. The effect of excess air infiltration attributed to tube failure close
to peephole door (refer figure 2). Furthermore, intermittent running of boiler due to various unplanned and annual shutdown accelerates
condensation of gaseous acid during cooling. An estimation of dew point temperature (T, °C) from flue gas according to equation 10 [32] shows
increase in partial pressures of 𝐻2𝑂 and 𝑆𝑂3 increases dew point temperature. Flue gas composition, flue gas temperature and excess combustion
air is attributed to partial pressure of 𝐻2𝑂 and𝑆𝑂3.
T = 203.35 + 27.6 log 𝑝𝐻2𝑂 + 10.83 𝑙𝑜𝑔 𝑝𝑠𝑜3 + 1.06 (𝑙𝑜𝑔 𝑝𝑠𝑜3+ 8)2.19 (10)

Unfortunately, flue gas composition is unknown in present case; it is difficult to estimate dew point temperature of sulfuric acid accurately from
equation 10. However, for known sulfur (0.58 wt %) in fuel oil with 10-30% excess combustion air (refer table 2) dew point temperature is to be
267°F (132°C) according to Okkes graph (refer figure 11) [32]. However, actual tube metal temperature of the failed tube before failure was found
to be 140°C. Bahman ZareNezhad et al reported that equation 10 can under predict tube wall temperature for lower moisture concentration [31].
The mean temperature (Tmean, K) of bare economizer tube can also be determined according to equation 11 [33, 34].

Tmean = 0.5 [( tw + tFG - U (tFG - tw) ( 1

hw -
1
))]
hFG (11)

h𝑤and h𝐹𝐺are heat conduction coefficients inside and outside the tube in J/m2h.K, tw and 𝑡𝐹𝐺 are temperatures of water and flue gas of the tube in
K, and U, total heat conduction coefficient in J/m2h.K, which can be obtained according to equation 12 [34].
1 1 1
U
= h +h (12)
w FG

For bare economizer tubes h𝑤= 665.4J/m2h.K, h𝐹𝐺 = 44360J/m2h.K and according to equation 12, 𝑈=655.56J/m2h.K [34]. The water and flue gas
temperature were 411K (138°C) and 449K (176°C), and substitution of aforementioned values reveals tube metal temperature as 411.56K
(138.56°C). The average tube metal temperature (from thermocouple) near failure location is 140°C, which is close to the estimated temperature
according to equation 11. According to equation 11, it can be seen that tube wall temperature is fixed by inner feed water temperature rather than
flue gas temperature. It means even at high flue gas temperature, the condensation of sulfuric acid can still occur on cold tube walls. Therefore,
economizer tube temperature is most important design factor to avoid dew point corrosion in utility boiler. The results are in line with literatures
[9-21, 34, 35] and similar failures were also experienced in coal fired boilers, furnace ducts and stacks systems of petroleum refineries. The only
way to avoid flue gas corrosion is to deactivate the condensation of sulfur deposits and tube wall cleaning.
Hydro jetting with 10% NaOH solution will remove fire side sulfur deposits [4]. Improper draining after hydro jetting will result in dew
point corrosion. The boiler operating condition in continuous process industry conducive for sulfur to form sulfur bearing compounds which
penetrates through un-protective scale to have direct contact with metal (refer figure 7c & figure 12). A power and boiler industry classifies this
type of corrosion as “cold end chemical corrosion” [13]. The correct choice of external coating in tube prevents from this corrosion but improper
coating may affect heat transfer. From economizer bank the flue gas pass through stack via duct pipe and emit to atmosphere. In order to avoid dew
point corrosion in stack, boiler stack has been internally lined with 50%Al2O3 refractory while externally insulated [35, 36]. Insulation holds
temperature and avoids drastic temperature reduction to prevent dew point corrosion on stack (refer figure 13).

Outer wall surface Sulfur compound condense Tube perforation starts Complete tube wall perforated

BFW leakage

Inner wall surface Fire side deposits T<= Dew Point

Figure 12 Schematic of dew point corrosion failure mechanism.

Boiler stack

Compressor
blower

Boiler

Steam
(product)

BFW pipeline

Figure 13 Restoration of utility boiler after shut down

6. Conclusions and recommended practices
Fuel containing sulfur is important factor for premature failure of boiler tube. In addition, water side corrosion is excluded. Economizer
tube made of carbon steel affected by dew point corrosion. At lower operating temperature below 150°C, the sulfur present in flue gas reacts with
moisture in fire side of boiler environment to form diluted sulfuric acid is root cause of failure.
Based on conclusions some good engineering practices along with counter measures are recommended and accepted by company to avoid dew
point corrosion in this utility boiler.
1) Dew point corrosion will never appear above condensation temperature. Therefore, flue gas exit temperature and BFW inlet temperature is to be
operated above 160˚C and 140˚C, respectively, to avoid condensation.
2) Alternate to IFO sulfur free Natural Gas (NG) should be used as fuel. Desulfurizer is to be introduced to utility boiler and sulfur in flue gases should
be monitored and controlled. Addition of additives (neutralizing) on fire side can reduce acid formation. The chemical composition of flue gas is
to be measured at periodic intervals and flue gas reheat can retard condensation.
3) Water ingress, air infiltration and ambient air leak through vent, peep door, casing hole (economizer zone) is to be eliminated. The cap cover should
be fixed on stack top retards rain water inside boiler stack.
4) Hydro jetting with 10% NaOH solution is to be carried to clean fire side acidic salt deposits with proper draining systems. Fire side SS304 metallurgy
is to be replaced with existing carbon steel.
5) Also, proper monitoring of super heater and evaporator tubes to be implemented as flue gases might affect superheater and evaporator tubes when
considering flue gas path.
6) Acid dew point temperature (ADT) sensor shall be used in economizer zone to monitor and process optimization.

After implementation (except recommendation No: 6), the boiler has been in service nearly for 2 years (until now) without leakage or severe
corrosion.

Future scope of improvement

 Modification of utility boiler operating conditions is not easy and development of corrosion resistant stainless steels is needed for prevention of
sulfuric acid dew point corrosion. Further, developed materials shall be exposed to actual boiler working conditions to investigate for material
substitution.
 The relation between SO3 in flue gas, catalytic action of fire side deposits and corrosion rate may be established for SS304 and SUS310S austenitic
stainless steels.

Acknowledgement
This work was performed during author previous employment in Numaligarh Refinery (A Group Company of Bharat Petroleum Corp.
Ltd), Assam and acknowledges Director-Technical, NRL-BPCL for providing fund to conduct this study. The author thanks quality control
department for providing various facilities to perform this study. Author also acknowledges Director, CMERI-CSIR for his encouragement to
publish this work. The author gratefully acknowledges the anonymous reviewers for many valuable suggestions.

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 Highlights

Deterioration of economizer tube in utility boiler

1. High sulphur content was detected in fire side deposits.

2. Acid dew point corrosion was root cause of failure.
3. Failure mechanisms were proposed for corrosion damage.
4. Control of sulfur content and raising the operating temperature of economizer tube were
put forward.
Conflict of interest

The author declares no known competing financial interests or personal relationships that
could have appeared to influence the work reported in this paper.