Engineering Failure Analysis 33 (2013) 2936

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Engineering Failure Analysis

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

Sulfuric acid dew point corrosion in waste heat boiler tube for
copper smelting furnace
R. Ebara a,, F. Tanaka b, M. Kawasaki c
a

Department of Mechanical System Engineering, Hiroshima Institute of Technology, 2-1-1, Miyake, Hiroshima 731-5193, Japan
Overseas Technical Sales Department, Mitsubishi Materials Corporation, 1-3-2, Ohtemachi, Tokyo 100-8117, Japan
c
Naoshima Smelter Renery, Mitsubishi Materials Corporation, Naoshima-Cho, Kagawa 761-03110, Japan
b

a r t i c l e

i n f o

Article history:
Received 22 January 2011
Received in revised form 31 March 2013
Accepted 3 April 2013
Available online 24 April 2013
Keywords:
Waste heat boiler tube
Sulfuric acid dew point corrosion
Scale
General corrosion
Corrosion resistant materials

a b s t r a c t
This paper presents the sulfuric acid dew point corrosion found on waste heat boiler tube
for a copper smelting furnace. Macroscopic and microscopic observation results for the
failed boiler tubes are shown. Then the analyzed results by X-ray uorescence, X-ray diffraction and EPMA on failed boiler tubes are demonstrated. Finally effective alloying elements for waste heat boiler tube material against sulfuric acid dew point corrosion are
briey described on the basis of the exposure test results for three kinds of steels in the
radiation section of the waste heat boiler.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Corrosion control in boiler tubes is one of the very important issues for safety and effective operation of boiler. So far various kinds of corrosion behavior in boiler tubes are reported on the basis of results by failure analysis and experiments. In
general the major causes of boiler tubes corrosion failure are classied into high temperature corrosion [13], molten salt
induced corrosion [46] and sulfuric acid dew point corrosion [79]. The most of the recent boiler tube corrosion have been
observed under boiler operation with more aggressive environments than those before. Therefore the failure analysis performs very important role to clarify the cause of boiler tube corrosion in the actual boiler.
In this paper it is reported on the sulfuric acid dew point corrosion behavior observed on leaked waste heat boiler tubes at
Naoshima Smelter of Mitsubishi Materials Corporation almost four years ago. The desirable materials for waste heat boiler
are briey touched on the basis of exposure test results of a couple of steels in the radiation section of the waste heat boiler.
2. Experimental procedure
2.1. Boiler exhaust gas condition
The outline of the waste heat boiler for copper smelting furnace is schematically shown in Fig 1. The temperature and the
gas ow rate of boiler exhaust gas was 1513 K and 36,000 Nm3/h, respectively. The exposed gas was mainly composed of 34%
SO2, 5%O2, 14%H2O and 39.5%N2. The boiler water temperature was 523 K.
Corresponding author.
E-mail address: ebara@gold.megaegg.ne.jp (R. Ebara).
1350-6307/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.engfailanal.2013.04.007

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R. Ebara et al. / Engineering Failure Analysis 33 (2013) 2936

Fig. 1. Outline of waste heat boiler for copper smelting furnace.

Table 1
Chemical compositions of STB340 (mass%).
Material

Si

Mn

STB340

<0.18

<0.35

0.3036

0.035 max.

0.035 max.

2.2. Boiler tube material

The boiler tube material was STB340. Chemical compositions and mechanical properties of the STB340 are shown in Tables 1 and 2, respectively.
2.3. Experimental procedures on cut out boiler tubes
The cut out screen tube surfaces were macroscopically observed by naked eyes. The cross section of the screen tube was
observed by optical microscopy. Corrosion products on the boiler tube were analyzed by X-ray uorescence and X-ray diffraction method. The scale formed on the boiler tube surface was analyzed by EPMA.
2.4. Exposure test
In order to nd a steel substitute for STB340 steels such as STB410, S-Ten1and SUS310S were exposed at the manhole
installed on the water-wall of the screen tube bank in radiation section for about one year. Chemical compositions of these
steels are shown in Table 3.

Table 2
Mechanical properties of STB340.
Material

Yield strength ry (MPa)

Ultimate tensile strength rB (MPa)

Elongation e (%)

STB340

175

375

35

Table 3
Chemical compositions of exposed steels (mass%).
Material

Si

Mn

Cu

Sb

STB410
S-Ten
SUS310S

0.32
0.02
0.08

0.35
0.27
1.5

0.55
0.95
2.0

0.035
0.11
0.045

0.035
0.011
0.03

0.29

0.10

Ni

Cr

20

25

R. Ebara et al. / Engineering Failure Analysis 33 (2013) 2936

31

Fig. 2. Investigated screen tubes.

3. Results and discussion

3.1. Examination on failed boiler tubes
3.1.1. Surface and corrosion products
Two manholes shown in Fig. 2 were examined. Blue and green colored corrosion products can be identied on the surface
of the manhole by naked eyes. Seven screen tubes of (ag) shown in Fig. 2 was cut out for examination. Yellow green and

Fig. 3. Surface appearance of tube (a).

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R. Ebara et al. / Engineering Failure Analysis 33 (2013) 2936

Fig. 4. Surface appearance of tube (b).

Fig. 5. Corrosion products detached from tube (b).

Table 4
Detected elements by X-ray uorescence analysis.
Major elements

Minor elements

Extremely small elements

Cu, Fe, S, Ca

Mo, Si, Br, Pb, K, Cd, Zn, Al Tl, As

Bi, Sn, Mn, Ti, V, P, Cr, Ni

Table 5
Chemical compounds identied by X-ray diffraction.
Identied chemical compounds

Presumable chemical compounds

CuSO45H2O
CaSO4
CaSO42H2O
FeSO45H2O

Fe3O4
CuO
MoS2
SiS2
CaS

R. Ebara et al. / Engineering Failure Analysis 33 (2013) 2936

33

Fig. 6. Cross section of tube (a). (a) Cross section of the tube. (b) EPMA analyzed area bracketed in (a).

blue colored corrosion products can be identied on all boiler tube surfaces. Corrosion products and cross section were
examined on boiler tubes (ad). Surface appearance of tubes (a and b) is shown in Figs. 3 and 4, respectively.
Corrosion products taken from tube (b) are shown in Fig. 5. Analyzed results by X-ray uorescence are summarized in
Table 4. The major elements detected were Cu, Fe, S and Ca. The minor elements and extremely small elements are supposed
to come from raw materials in copper smelting operation and fuel in boiler burning. Table 5 shows results by X-ray diffraction. Chemical compounds such as CuSO4, CaSO4 and FeSO4 were identied. Presumable chemical compounds were Fe3O4,
CuO, MoS2, SiS2 and CaS.
3.1.2. Cross sectional observation
Minimum thickness of the tube (a) was about 2 mm. Original thickness of this tube was 5 mm. Therefore corrosion rate of
this tube can be estimated to be approximately 0.3 mm/year for 10 years service of this boiler. Cross section observed by SEM
is shown for tube (a) is shown in Fig. 6. It is obvious that corrosion initiated at the outer surface of the tube. General corrosion
was observed and pitting corrosion was not observed on the surface of the tube. The rm scale 7501500 lm thick was adhered on the corroded area of all observed tubes. The map of elements for the matrix and the scale of specimen (a) is shown
in Fig. 7. Distribution of the elements such as C, Fe, O, Cu, S and Ca can be observed on the scale. Other elements were Al, Si, K,
Zn, As, Mo and Cd. Quantity of element such as C, O and Fe near the matrix was approximately same as those on the surface
of the scale. The S content in the scale was larger than that in the matrix. The Cl content was very small both in the matrix
and the scale. These results for tubes (ad) are summarized in Table 6.
3.2. Cause of the screen tube failure
It is clear from the above mentioned examination that corrosion initiated at the outer surface of the boiler tube. Corrosion
form is general corrosion without pitting. Relatively thick scale 7501500 lm thick was adhered on the outer surface of the
boiler tube. The scale was not porous and looks to be rm. It can be considered from EPMA analysis on cross section that the
contributed elements to corrosion are S, Fe and O. The S and Fe were major elements composed of corrosion products. Therefore it can be concluded that S has prominent effect on general corrosion of the boiler tubes.
So far many papers have been reported on corrosion failure of boiler tubes. The primary causes of corrosion failure in boiler tubes are classied into high temperature corrosion, molten salt induced corrosion and sulfuric acid dew point corrosion.
High temperature corrosion most frequently occurs on utility power boiler tubes [1]. This corrosion is strongly related to a
Na and V in fuel and is quite different from that observed in this examination. Molten salt induced corrosion occurs in waste
incineration boiler. In this corrosion Cl in molten salt contribute to corrosion of boiler tube [10]. In this examination Cl content found in the scale was very few. Cracks that features molten salt corrosion were not observed on the scale. Thus corrosion in this examination is quite different from high temperature corrosion and molten salt induced corrosion. On the

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R. Ebara et al. / Engineering Failure Analysis 33 (2013) 2936

Fig. 7. EPMA analysis for cross section of tube (a).

Table 6
Detected major elements by EPMA analysis (wt%).
Position

Si

Cl

Cu

Ca

Fe

Mo

(a) Matrix
Scale
(b) Matrix
Scale
(c) Matrix
Scale
(d) Matrix
Scale

47.7
44.0
21.9
17.5
20.6
22.7
50.7
41.3

10.3
11.8
23.9
20.9
28.2
19.4
21.4
27.5

1.5
2.5
5.1
5.7
8.8
10.5
5.9
8.5

10.1
14.3
0.8
3.7
3.2
6.2
0.6
0.1

0.2
0.2
0.3
0.2
0.5
0.2
0.2
0.5

0.8
2.2
2.3
1.1
4.2
1.4
1.8

0.2

28.3
23.2
38.2
42.3
26.1
29.4
9.9
16.4

0.5
0.4
3.6

1.4
1.6
1.9

Note: the other elements such as Na, Al, P, K, Cr, Mn, Ni, Zn, As, Ag and Cd were excluded in this Table.

other hand the sulfuric acid dew point corrosion is well known low temperature corrosion phenomenon [9]. In this boiler
H2SO4 is produced by the reaction with gaseous SO3 in gas and H2O. Then FeSO4 found by X-ray analysis can be produced
by the reaction with H2SO4 and boiler tube.
That is to say the sulfuric acid dew point corrosion occurs by following reaction.

R. Ebara et al. / Engineering Failure Analysis 33 (2013) 2936

35

Fig. 8. Cross section of exposed materials. (a) STB410 and (b) SUS310S.

SO3 H2 O ! H2 SO4
Fe H2 SO4 ! FeSO4 H2
In fact the manhole in this boiler was opened for about two hours per week in order to remove an accretion on the wall.
Moreover, every two months, the manhole was opened for less than 24 h in order to maintain of the copper smelting plant.
During these periods the furnace was heated by burner in order to keep melt temperature while the boiler operation was
halted. Therefore the boiler tubes experienced cyclic repeat of heating and cooling for about ten years. As a result general
corrosion formed on the outer surface of the boiler tubes due to sulfuric acid dew point corrosion. It can be concluded that
the reduction of the boiler tube thickness due to sulfuric acid dew point corrosion was the major cause of the water leakage
from the boiler tubes.
3.3. Exposure test in the waste heat boiler
It was concluded from examination that the major cause of the boiler tube failure was sulfuric acid dew point corrosion. It
is not easy to modify the boiler operating condition with copper smelting operation. Consequently it is reasonable to modify
the boiler tube material to prevent sulfuric acid dew point corrosion of the boiler tube.
After one year exposure test the specimen surface of the exposed steels was colored yellow and blue green as same as that
observed on failed boiler tube. The same scales observed on failed boiler tubes were formed on the exposed specimen surfaces. The typical examples of the scales are shown for STB410 and SUS310S in Fig. 8. General corrosion was apparently observed for these steels. The thickness of the scale for STB410, SUS310 and S-Ten1 was 425, 200 and 250 lm respectively.
Among these tested steels the thickness of the scale was the smallest for SUS310S. From EPMA analysis for scale (A in
Fig. 8) and matrix (B in Fig. 8) Fe and S were mainly detected on the scale. The results by X-ray uorescence and X-ray diffraction showed that these exposed specimens were suffered from sulfuric acid dew point corrosion during exposure in the
boiler.
General corrosion that features sulfuric acid dew point corrosion is most frequently observed in the inner wall of the steel
stack [11] and the element of an air heater [12,13].

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R. Ebara et al. / Engineering Failure Analysis 33 (2013) 2936

One of the authors evaluated corrosion resistance of various kinds of steels under heavy oil red smoke stack environment and developed corrosion resistant stainless steels such as YUS260 and YUS270 that keep maintenance-free of smokestacks linings [14,15]. Consequently it was claried that alloying elements such as Cr, Ni, Mo and Cu are effective to prevent
general corrosion of steels under sulfuric acid dew point corrosion environment. Therefore SUS310S may substitute STB340
for boiler tube material.
4. Concluding remarks
In this paper it is reported on the failure analysis on the waste heat boiler tubes for copper smelting furnace. It can be
concluded from the metallurgical investigations that the cause of the boiler tubes failure is the sulfuric acid dew point corrosion due to air leakage and cyclic temperature prole. Development of corrosion resistant materials is desirable to prevent
sulfuric acid dew point corrosion in waste heat boiler tubes.
Acknowledgements
The authors thank Dr. Yoshio Harada, Tocalo Co., Ltd., Prof. Fujimitsu Masuyama, Kyushu Institute of Technology and Dr.
Yuuzou Kawahara, Inspection and Research laboratory Co., Ltd. for their useful suggestions and fruitful discussions.
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