Alkaline-Type Boiler Tube Failures Induced by Phosphate Water Treatment

Moavinul Islam, CC Technologies Inc.

From: Handbook of Case Histories in Failure Analysis, Vol 2, K.A. Esakul, Ed., ASM International, 1992
Abstract: Tube failures occurred in quick succession in two boiler units from a bank of six boilers in a refinery. The failures were
confined to the SAE 192 carbon steel horizontal support tubes of the superheater pack. In both cases, the failure was by perforation
adjacent to the welded fin on the crown of the top tubes and located in an area near the upward bend of the tube. The inside of all the
tubes were covered with a loosely adherent, black, alkaline, powdery deposit comprised mainly of magnetite. The corroded areas,
however, had relatively less deposit. The morphology of the corrosion damage was typical of alkaline corrosion and confirmed that the
boiler tubes failed as a result of steam blanketing that concentrated phosphate salts. The severe alkaline conditions developed most
probably because of the decomposition of trisodium phosphate, which was used as a water treatment chemical for the boiler feed
water.

Keywords: Alkaline corrosion; PH; Water chemistry

Material: SAE 192 (Nonresulfurized carbon steel)
Failure type: High-temperature corrosion and oxidation

Background

Unscheduled shutdowns occurred in boilers No. 1 and No. 3 from a bank of six boiler units in a refinery, due to failure of
the horizontal support tubes (Type SAE 192 carbon steel) of the superheater pack. Figure 1 shows a detailed sketch of the
support tubes and the location of the failures. The support tubes are arranged in three rows with horizontal and vertical
sections. Each row has two tubes fixed one on top of another with welded support plates. The bottom of the superheater
pack is welded with fins to the top tubes of the horizontal support.

Fig. 1 Schematic of superheater support tubes showing location of maximum corrosion damage

In Boiler No. 1, failure occurred on the top tubes of the first and the third row of the horizontal support; in Boiler No. 3,
the top tube of the first row failed. In both cases, the failure was by perforation adjacent to the welded fin on the crown
(or roof) of the top tubes, located in an area near the upward bend of the tube.

Applications

The boilers have a maximum continuous rating of 163 Mg/h (180 ton/h) with an average operating load of 109 Mg/h (120
ton/h) and an average operating pressure of 6.2 MPa (900 psig). The internal temperature of the main bank tubes is 275
C (527 F) while the superheater steam temperature is 450 C (842 F).
Demineralized make-up water/condensate return is deaerated and then injected with hydrazine and amine before entering
the boiler feed pumps. Trisodium phosphate (Na3PO4) is injected into the boiler drum. Continuous and intermittent
blowdown facilities are installed in the boiler drum.

Specimen selection

The tube sections selected for failure analysis were: Boiler No. 1, Support No. 1 (failed); Boiler No. 3, Support No. 1
(failed); and Boiler No. 3, Support No. 3 (not failed but with corrosion from inside). For purposes of identification, these
tubes are referred to here as B1Sl, B3S1, and B3S3, respectively.

Visual Examination

The average diameter of the tubes was 56.7 mm (2.23 in.), and the average wall thickness was 5.9 mm (0.23 in.). No
outside bulging of the tubes was apparent. The outer part of the tubes had a thin adherent oxide, dark brown to black in
color.

All three sections were cut longitudinally for closer examination. Samples BlSl and B3S1 had the maximum corrosion
damage which was confined to the crown (inside top or roof) of the tube in the form of gouging and a deep trench
following the line of the welded fin. The bottom half of the tubes did not show any corrosion damage. Fig. 2 shows the
type of attack observed on both tubes. The corrosion trench had actually gone through the thickness of the tube and into
the welded fin. This type of severe attack was confined to an area about 30 cm (11.8 in.) near the upward bend of the
horizontal tube with less attack in the adjacent area on the right (Fig. 3). The horizontal tubes are approximately 2.5 m
(8.2 ft) long. No attack was observed at the end where these tubes bend downwards (see Fig. 1). Sample B3S3 showed
less severe attack, shown in Fig. 4.

Fig. 2 Deep gouging (trenching) type of attack in the inside upper part of Tubes BlSl and B3S1
Fig. 3 Less severe corrosion damage in an adjacent part to the right of the area shown in Fig. 2

Fig. 4 Gouging type of attack in Tube B3S3 on the inside top part

The inside of all the tubes were found to be covered with a very loosely adherent, black, powdery deposit. However, the
corroded areas had relatively less amounts of deposit.

Testing Procedure and Results

Surface examination

Scanning electron microscopy was used to study the morphology of the corroded surface, while EDX analysis
was carried out on the corroded areas to identify various elements in the corrosion products. Figure 5 shows a
representative EDX spectrograph. The main peaks were due to Fe but minor peaks due to Cu, Ca and P were also seen.
Fig. 5 Representative EDX spectra taken in a corroded area at part the boiler tube

Metallography

Cross-sectional and logitudinal sections were cut from Samples B1S1, B3S1, B3S3 near the corroded areas. After
preparation and etching with nital, they were examined under the optical microscope. Figure 6 shows a low-magnification
cross-sectional view of Sample B3S1 showing the corrosion trench which had gone through the tube material and into the
welded fin. The same type of attack was observed in sample B1S1. Figure 7 shows a longitudinal section of Sample B3S1
from a less severely attacked area. The gouging attack is apparent.

Fig. 6 Deep trench-like attack, which had gone through the tube material and into the welded fin,
representative of type of attack in Tubes BlS1 and B3S1.
Fig. 7 Gouging attack in a longitudinal section from a corroded area in Tube B3S1. Note lack of weld
fusion between tube material and fin.

Except for some lack of fusion observed between the weld bead and the parent metal (Fig. 6), no microstructural
abnormalities were observed area of corrosion damage or in other sections of the tube.

Chemical analysis/identification

Corrosion Deposits. The black powdery deposit was scraped from the tubes and analyzed with the help of X-ray
diffraction (XRD) which indicated that the deposit was mainly composed of Fe3O4 (magnetite).

Some of the scraped products (about 1 g or 0.04 oz.) was leached wit about 25 ml of hot double distilled water. The pH of
this water extract was then measured. An increase in the pH value from 6.5 (pH of the distilled water) to 8.4 was
observed, indicating that the deposit was alkaline.

Discussion

The literature on boiler corrosion failures was reviewed to rationalize the findings of the present investigation and to
suggest a plausible explanation for the observed severe corrosion damage of the boiler tubes.

As mentioned earlier, the most severely corroded part of the tubes had a trench-like appearance on the roof (or crown) of
the tube which also coincided with the bottom of the welded fin. Since the tubes are horizontal and there is two-phase
flow, the corrosion had occurred in the steam phase. An identical example of boiler tube corrosion with photographic
documentation could not be found in the literature. However, it is mentioned that in horizontal or inclined tubing,
insufficient mass velocity can allow the flow of steam bubbles along the top of the tube (steam blanketing) and cause a
strip along the top of the tube to slowly thin due to caustic attack, ultimately leading to perforation (Ref 1).

Under proper operating conditions, boiler tubes develop a two-layer magnetite (Fe3O4) layer (Ref 2) according to the
reaction:

3Fe + 4H2O) Fe3O4 + 4H2 (Eq 1)

Ferrous hydroxide, Fe(OH)2, is believed to be the intermediate in this process, converting to magnetite above 100 C
(212 F) according to the Sticker reaction (Ref 3):
 3Fe(OH)2 Fe3O4 + H2 + 2H2O (Eq 2)

The inner layer is relatively thick, compact, adherent and continuous while the outer layer is thinner, porous and powdery
in texture. Counter currents of ions set up between the metal surface and the aqueous environment are responsible for the
growth of the oxide layers (Ref 2). Reactions at the metal/oxide interface result in the growth of the compact Fe3O4. The
outer porous oxide is formed Fe+2 ions migrating outward react with OH- ions at the oxide/solution interface to give
Fe(OH)2, which then converts to Fe3O4 as indicated above. The different conditions under which the two magnetite
layers are formed result in their different morphologies. Porous magnetite is formed under alkaline conditions. Strong
alkaline conditions can lead to dissolution of the magnetite and enhanced corrosion of the iron.

The porous and powdery magnetite deposit indicates that alkaline conditions must have existed in the boiler tubes. This
observation is also supported by the fact that the water extract of the magnetite deposit was found to be slightly alkaline.

The morphology of the corrosion damage in the present case is apparent from Fig. 2, 3, 4, 5, 6. The features may be
considered typical of alkaline corrosion or chelant attack. However, since no chelates (e.g., EDTA) were used in these
particular boilers, chelant attack can be discounted. Alkaline attack most likely occurred due to steam blanketing in an
area of high heat flux, in this particular case, the welded fin on the top tubes. The bottom tubes do not have a similar area
of high heat flux because of the geometry and location as well as the presence of a liquid phase, hence the absence of
corrosion attack on the bottom tubes. A similar case of severe corrosion has been cited for studded tubes of baker's ovens
(Ref 4) where the attack was observed to occur at the base of the welded studs. The cause was attributed to an abnormally
high heat flux through the studs leading to local boiling and concentration of boiler salts, in particular NaOH. Alkaline
attack then occurred.

The source of the NaOH causing alkaline attack is the trisodium phosphate (Na3PO4), used as one of the boiler water
chemicals. It has been reported (Ref 1, 5) that when a solution of trisodium phosphate is concentrated at elevated
temperature, crystals of disodium phosphate (Na2HPO4) precipitate out and the supernatant liquid is rich in NaOH.

Na3PO4 + H2O Na2HPO4 + NaOH (Eq 3)

To eliminate the formation of free caustic, a mole ratio of Na to PO4 of 2.6 is recommended. This is accomplished by
adding a mixture of Na3PO4 and Na2HPO4. A ratio of 65% Na3PO4 to 35% Na2HPO4 corresponds to a mole ratio of 2.6
(Ref 5).

The mole ratio of Na to PO4 in Na3PO4 is 3. Judging from the occurrence of alkaline corrosion in the present case, boiler
operating conditions have led to the decomposition of trisodium phosphate to free caustic according to the equation
above. Based on the existing literature, a coordinated phosphate or a congruent method of water treatment (Ref 1, 5)
under the present circumstances would have possibly avoided the problem. It may be recalled that the refinery used only
trisodium phosphate in its boiler water.

Although the pH of the bulk water may be in the safe range (i.e. between 9.5 to 10.5), the occurrence of hot spots and
steam blanketing leads to the concentration of salts, so that highly alkaline conditions can be established for boilers that
use Na/PO4 ratios of 2.6 or less.

The occurrence of hot spots and areas of high heat flux in boiler tubes can lead to the formation of thermogalvanic cells
where hotter areas act as the anode and suffer accelerated corrosion. Such a situation has been reported by some authors
in the corrosion of boilers. Thermogalvanic effects would certainly enhance the alkaline corrosion observed in the present
case.
Small amounts of copper were detected by EDX on the corroded surface (Fig. 5). The presence of copper and copper
oxides are known to create anodic sites on iron (Ref 6, 8). In the present case, the presence of copper possibly contributed
to the overall corrosion process. Although copper was detected by the EDX technique, XRD analysis of the deposits
failed to pick up any copper compounds, possibly because the amount present was below the detection limit.

Conclusion

The configuration of the superheater support tubes with its welded support plates, gave rise of hot spots and areas of high
heat flux, resulting in steam blanketing. The morphology of the corrosion damage confirmed that the boiler tubes failed as
a result of steam blanketing that concentrated the phosphate salts resulting in alkaline attack.

The powdery non-adherent magnetite deposit on the tube internals as well as its alkaline characteristics indicate that too
severe an alkaline conditions developed most probably due to the decomposition of trisodium phosphate to free NaOH
because of steam blanketing in areas of high heat flux.

References

1. Principles of industrial Water Treatment, Chapters 11 to 14, Drew Chemical Corporation, Boonton, NJ, 1981.
2. E.C. Potter and G.M.W. Mann, The Fast Linear Growth of Magnetite on Mild Steel in High Temperature
Aqueous Conditions, Corrosion, Vol. 21, 1965, p 5767.
3. U.R. Evans, The Corrosion and Oxidation of Metals, Chapter XII, Secondary Supplementary Volume, Edward
Arnold, London, 1976.
4. F.R. Hutchings, On-load corrosion in Tubes of High Pressure Boilers, in Failure Analysis: The British Engine
technical Reports, American Society for Metals, Metals Park, OH, 1981, p 2848.
5. C.G. Bozeka and F.J. Pocock, Waterside Corrosion Control in Industrial Boilers, CORROSION / 85, Paper No.
249, NACE Corrosion Conference, Boston, MA, 1985.
6. D. R. Holmes and G.M.W Mann, A Critical Survey of Possible Factors Contributing to Internal Boiler
Corrosion, Corrosion, Vol. 21, 1965, p 3948.
7. R.H. Bailey, M.J. Esmacher and T.L. Warner, Aqueous Corrosion in Boilers: Analysis and Mitigation, Power
Engineering, Vol. 34, 1985, p 3340.
8. J.P. Engle and C.E. Fox, The Role of Copper and Physico-chemical Factors in Steam Generator Tube Failures,
SE Electric Exchange, Beloxi, MS, April 1958.

Related Information

D.N. French, Failures of Boilers and Related Equipment, Failure Analysis and Prevention, Vol 11, ASM Handbook, ASM
International, 1986, p 602627

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