Werkstoffe und Korrosion 39, 69-83 (1988)
corrosive environment. Manufacturing and testing of the coex-
truded tubes for power industry has been recently a subject of
intensive investigations [7]. It is expected that some field tests
will be carried out in the nearest future.
As regards slagging problems in the pcf boilers it is proposed
to use mineral additives in order to reduce the amount of
deposits accumulating on tube surfaces or to make them more
friable and easier to remove. One of possible solutions consid-
ered is to add ultra fine dispersions of dolomite. First trials
with this additive are expected also in the nearest future.
To sum up, in recent years numerous and many-sided
studies have been undertaken in Poland to ameliorate the
performance and availability of pcf electric utility boilers. It is
believed that the materials solution consisting in the applica-
tion of bimetallic tubes as well as the adequate dosage of addi-
tives in coal combustion process will finally lead to the desired
extension of plant life.
Recent plant experience and research into fireside
corrosion in Japan
Neuere betriebliche Erfahrungenund Forschungsarbeitenauf dem Gebiet der
feuerseitigen Korrosion in Japan
The increasing use of heavy oil as a fuel in power stations has given
rise to intensified research in the field of fireside corrosion in Japan.
The problems which have to be tackled are described in terms of
experiences gained in the operation of oil and coal fired boilers. The
main types of damage encountered are nonuniform wastage of tubes in
connection with carburization. In this context significant interdepend-
ences have been found in connection with coal deposition (especially
sodium and sulphur contents). On the basis of this experiences and of
the results of corrosion tests in the laboratory and in the field it has
been found that the measure offering the best prospect for corrosion
control might be the use of coextruded tubing which would allow a
combination of high corrosion resistance and high creep strength. In
addition to that some modified alloys (e.g. Alloy 800H, CR30A or
NF709) offer an interesting potential whereby the high chromium con-
tent (more than 20%) is the main criterium.
Introduction
Japanese total electricity production in 1985 was 617,952
million kwh and 63.2% of that was by thermal power. The
* Shigemitsu Kihara, Akira Ohtomo, Ichiro Kajigaya (Boiler Div.),
Fumihiro Kkhimoto (Boiler Div.), Ishikawajima-Harima Heavy
Industries Co., Ltd., Research Institute, 1-15, Toyosu 3-chome,
Koto-ku, Tokyo 135, Japan.
~~ ~ ~
0 VCH Verlagsgesellschaft mbH, D-6940 Weinheim, 1988
Recent plant experience 69
References
[l] M . Danielewski, E. Godlewska, K. Godlewski, S . Mrowec:
Report on Fireside Corrosion of pcf Utility Boilers, Contract No.
2.342.25 coordinated by Central Office for Technological Devel-
opment, 1986.
[2] S. Brooks, D. B. Meadowcroft, in: Corrosion Resistant Materials
For Coal Conversion Systems, Ed. by D. B. Meadowcrofi and M.
I . Manning, Applied Sci. Pub. Ltd. (1983) 105-120.
[3] ibid. pp. 87-103 ( P . Mayer, A . V. Manolescu, S. J . Thorpe).
[4] R. J. Fruehan, L. J . Martonik: Met. Trans. 4 (1973) 2793.
[5] R. J. Fruehan, L. J. Martonik: Met. Trans. 4 (1973) 2783-92.
[6] R. A. Rapp, K . S. Goto in: Proc. Symp. on Corrosion in Fused
Salts, Electrochem. SOC.,Princeton, NJ, 1979.
[7] H . Dyja: Report on coextruded Tubes Manufacturing, Contract
no. 2.342.25 coordinated by Central Office for Technological
Development, 1986.
(Received: 04.09. 1987) W 2546
S. Kihara, A. Ohtomo, 1. Kajigaya and F. Kishimoto*
Die wieder zunehmende Verwendung von Schwerol zur Beheizung
von Kraftwerken hat in Japan zu einer Intensivierung der Forschung
auf dem Gebiete der feuerseitigen Korrosion gefiihrt. Die Probleme,
die dabei zu behandeln sind, werden aufgrund der Erfahrungen darge-
stellt, die sich beim Betrieb von ol- und kohlebeheizten Kesseln erge-
ben haben. Hauptsachlich wurden dabei ungleichmaBige Abtragungen
an Rohren, verbunden mit Aufkohlung gefunden, wobei sich signifi-
kante Abhangigkeiten von der Kohlezusammensetzung, vor allem
dem Natrium- und Schwefelgehalt, ergaben. Aufgrund dieser Erfah-
rungen und zahlreicher Korrosionsversuche im Laboratorium und
unter Betriebsbedingungen wurde festgestellt, daB die aussichtsreich-
ste Maanahme zur Bekampfung der Korrosion in der Venvendung in
coextrudierten Rohren bestehen konnte, da dann die Kombination
von hoher Korrosionsbestandigkeit und hoher Kriechfestigkeit reali-
sierbar wird.
Daneben bieten auch einige modifizierte Legierungen (z. B. Alloy
800H, CR30A oder NF709) gute Aussichten, wobei der hohe
Chromgehalt (iiber 20%) das entscheidende Kriterium ist.
total capacity of thermal power units installed is 110 million
kw. As to the fuel of thermal plants, consumption of LNG and
coal have increased and heavy oil decreased in the last five
years as shown in Fig. 1. As, following recommendations by
IEA. new oil-fired Dlant is not constructed, the uroDortion of
I . I
LNG and jncreaSein the future*
AS Can be Seen in an eXampk demonstrating the changes Of
chemical composition of the fuel used in an oil-fired boiler
(Fig. 2 ) , low sulfur oil has been used since the early '70ies in
0043-2822/88/0202-0069$02.50/0
70 Kihara, Ohtomo, Kajigaya and Kishimoto Werkstoffe und Korrosion 39, 69-83 (1988)

heater and reheater tubes. Recently 9 Cr-1Mo steel (SA 213-

T91) has been used for new plant and tube replacement
because of its excellent high temperature strength and its low
price.
Research work aimed at improvements in coal-fired plant
and at high efficiency has been very active in these several

5-
.-
0
1

251 \ Heavy oil

years. The authors of this paper are responsible for a laborat-
ory test on coal-ash corrosion (Task 7-1 of EPRI Research
Project 1403-19, "Boiler R&D for improved coal-fired
plants"). Abundant research reports on coal-ash corrosion
[l-41 and the development of new material technologies
including co-extruded and coated tubes [5-101 have been pub-
Crude oil lished in these years.
In this paper recent plant experience with fireside corrosion
2 and research work on coal-ash corrosion and new material
technologies will be reported.

Plant experience
Superheater and reheater tubes
'81 '82 '83 '84 '85 Oil-fired plant (Case 1)
Year
Fireside corrosion on superheater tubes has been investi-
Fig. 1. Change of fuel used in thermal power plants in Japan gated for four years in the boiler whose specificationis shown
Abb. 1. Veranderungen bei der Verwendung von Brennstoffen in in Table 1. A heavy oillcrude mixture was fired in this boiler.
japanischen Warmekraftwerken The change of impurity content of the mixed fuel for the test
duration is shown in Fig. 3. It should be noted that the fuel is a
order to meet environmental regulations. Since the vanadium low corrosive one, i.e. low in S, Na and V. The internal tube
content is generally low in low sulfur oil and low excess air diameters at the test sites are shown in Fig. 4 with the metal
combustion has been applied to suppress NOx, catastrophic and gas temperatures in each site. Periodic measurements of
oxidation by vanadium compounds (V attack) has hardly been outer tube diameter and wall thickness, and chemical analyses
observed while sulfidation is frequently observed in fireside of deposit and scale on the tubes were performed during
corrosion. Since sodium and sulfur compounds are the predo- annual inspections. Chemical compositions of tubes (347H
minant components of deposits on superheater and reheater stainless steel) tested are shown in Table 2.
tube surfaces in vanadium containing oil combustion, sulfida- Distributions of wall thickness on the circumference of tubes
tion inevitably occurs. Moreover, low 02 and high S potential measured at the '82 inspection (after 11,351 hrs' service and
atmospheres created by low excess air combustion further pro-
motes the occurrence of sulfidation.
On the other hand, recently a trend towards some diversity
in fireside corrosion has appeared because high sulfur oil is
being used again, because antipollution equipments were
installed in most plants. However, the research work on 8r
fireside corrosion in oil fired seems to be inactive and the
replacement of tubes (on the basis of monitoring tube wall
thickness) has become an established measure to combat
fireside corrosion in Japan.
As to tube materials, carbon steel, low alloy steels (1.25 Cr-
1Mo and 2.25 Cr-1 Mo etc.) and austenitic stainless steels
(316 H, 321 H and 347 H) have been widely used for super-

8 1.5 h

o ~ ' " ' ' ' ' " ' ' 1

'72 ' 7 3 ' 7 4 '75 '76 '77 '78 '79'80'81 '82-'84
1981 1982 1983 1984 1985
Year Year

Fig. 2. Change of S content in fuel used in an electricity utility boiler Fig. 3. Change of impurity content of fuel burned in Case 1 boiler
Abb. 2. Veranderung des Schwefelgehalts im Brennstoff eines Kraft- Abb. 3. Veranderung im Gehalt an Verunreinigungen im Brennstoff
werkskessels fur den Kessel Nr. 1
Werkstoffeund Korrosion 39, 69-83 (1988) Recent plant experience 71

Fig. 4. Boiler stiucture and locations where corrosion

7 investigation was performed (Case 1)

I
1 Abb. 4. Kesselaufoau und Lage der fur Korrosionsver-
suche ausgewahlten Bereiche (Kessel Nr. 1)

211 startups and shutdowns) and '84 inspection (after tube at the inlet of plate superheater and the flame side of the
26,099 hrs' service and 211 startups and shutdowns) are shown tube at the outlet most severely corroded. Fig. 8 shows the
in Figs. 5, 6 and 7. The surface recession of plate superheater maximum surface recession as a function of exposure time. It
tubes after 4 years' service revealed that the rear side of the can be seen that the corrosion loss is higher in the plate
superheater than in the final stage superheater area, in spite of
the lower metal temperature. It is attributed to higher gas
Table 1. Specification of boiler (Case 1) temperature and easier deposit formation in the plate super-
Tabelle 1. Daten des Kessels Nr. 1 heater area. Anyhow, the maximum corrosion rate of 347H
tube is concluded to be fairly low (less than 0.10 mdyear) in
Capacity: 1210 t/h this atmosphere. Reference data [ll] for 347H and 321H
Steam pressure: 176 kg/cm* tested in a different boiler (max. steam temp. 569"C, mixed
Steam temperature: 571"C (outlet of superheater)
541"C (outlet of reheater) heavy and crude oil) are superimposed in Fig. 8. The corro-
Type: single drum, natural circulation sion rates of reference data and this study for 347H are in
good agreement. Although, unfortunately, no information

Table 2. Chemical composition of tubes tested

Table 2. Chemische Zusammensetzung der gepruften Rohre

location test year C Si Mn P S Ni Cr Nb

PSH 1 1982 0.07 0.46 1.58 0.027 0.006 12.30 18.15 0.76
1984 0.07 0.61 1.48 0.026 0.005 12.31 17.93 0.78
PSH 2 1982 0.08 0.54 1.44 0.028 0.004 12.70 17.70 0.83
1984 0.08 0.54 1.44 0.025 0.003 12.65 173 5 0.80
FSH 1 1982 0.08 0.53 1.44 0.027 0.004 12.65 17.75 0.84
1984 0.08 0.53 1.45 0.025 0.003 12.55 17.85 0.81
Spec. JIS SUS 347HTP* 0.04 61.00 S2.00 50.03 S0.03 9.00 17.00 Nb + Ta
-0.10 - 13.00 -20.00 8XC%-1.00

* Japanese Industrial Standard G 3463

72 Kihara, Ohtomo, Kajigaya and Kishimoto Werkstoffe und Korrosion 39,69-83 (1988)

5.2 -
-
-
-*--
'82 inspection ( 1 1,351 hr)
'84 inspection (26,099hr)

-+ ' 8 2 inspection (1 1,351 hr)

'84
-0- inspection (26.099hr)
5.4

7 8 1 2 3 4 5 6
-
I I I
Flame side Rear side
7 8 1 2 3 4 5 6 Location on circumference
Flame side Rear side
Fig. 7. Result of wall thickness measurements at eight points of the
Location on circumference
tube circumference in the final stage superheater at the '82 and '84
Fig. 5. Result of wall thickness measurements at eight points of the inspections
tube circumference at the inlet of a plate superheater at the '82 and '84 Abb. 7. Ergebnisse der Wanddickenmessungen an acht Punkten des
inspections Rohrumfangs in der Uberhitzerendstufe bei den Inspektionen 1982
Abb. 5. Ergebnisse der Wanddickenmessungen an acht Punkten des und 1984
Rohrumfangs am Eingang eines Plattenwarmeaustauschers bei den
Inspektionen 1982 und 1984

about the chemical composition of the fuel for the reference 1.7mrn at 1.8xlO'hr

data exists, the composition of deposit is similar as mentioned

later.
The reference data show that 347 H is superior to 321 H in
corrosion resistance. Fujikawa et al. [ll] have attributed this
to the long-term stability of Cr-Fe-0 protective scale formed
on 347H.
2
.5 1 i
i
___---
The result of chemical analysis of the deposits taken from
each site at the '82 and '84 inspections is shown in Table 3. The .'
.+- *--
deposit mainly consists of alkali sulfate and possesses a high
N a 2 0 N 2 0 5ratio. No low melting material was detected. This
table also suggests that the chemical composition of the 0
1x104 2x104 3x104
deposit for the reference corrosion data is similar to that of this
Time, hr.
study.
Fig. 8. Maximum surface recession for 347 and 321 SS as a function of
exposure time
5.21
Flame 1 Abb. 8. Maximale Wanddickenabnahme vom Stahl 347 und 321 in
L Abhangigkeit von der Betriebsdauer
5.1 1
I

5.01
E Electron and X-ray images of the tube surface areas for each
location are shown in Fig. 9, 10 and 11. Ni-Fe-Cr sulfide was
formed at the interface of base metal and scale. An Fe-Cr
5
._ 4.9 oxide scale is present on the sulfide and is enriched in Cr at the
5 interface with the sulfide scale. The existence of a protective
2 4.8 Cr-enriched oxide is supposed to contribute to the high corro-
sion resistance of 347 H. V and Na were detected throughout
4.7

4.6 L
- ' 8 2 inspection (1 1,351 hr)
' 8 4 inspection (26,099hr)
-a--
the outer layer of the oxide scale and in the deposit at the inlet
of the plate and final stage superheaters, but not at the outlet
of plate superheater. It is concluded that the existence of V
and Na in the scale does not always affect the corrosion rate.
7 8 1 2 3 4 5 6 Carburization which is often observed in corroded austenitic
Flame side Rear side stainless steels was not observed in this sample.
Location on circumference

Fig. 6. Result of wall thickness measurements at eight points of the

tube circumference of plate superheater outlet at the '82 and '84 in-
spections,
Abb. 6. Ergebnisse der Wanddickenmessungen an acht Punkten des
Rohrumfangs am Ausgang eines Plattenwarmeaustauschers bei den
Inspektionen 1982 und 1984
Oil-fired plant (Case 2)
Fireside corrosion of 316 H and 347 H superheater tubes was
followed for five and a half years in the boiler whose specifica-
tion is shown in Table 4. Three each test tubes of 316H and
Werkstoffe und Korrosion 39, 69-83 (1988) Recent plant experience 73

Table 3. Chemical composition of deposits on tubes tested (Case 1)

Tabelle 3. Chemische Zusammensetzung der Ablagerungen auf den gepriiften Rohren (Kessel Nr. 1)

location bottom plate SH top plate SH bottom final stage Ref. [11]*
year 1982 1984 1982 1984 1982 1984

pH(l g/100 ml H20) 5.4 5.4 5.6

total S as SO, (%) 47.0 48.5 47.6 51.5 48.3 54.0 48.3
total Fe as Fe20, (%) 2.2 3.6 2.2 1.9 2.2 1.1 4.8
total V as VzO, (%) 1.7 2.1 1.7 1.3 2.4 2.0 2.1
total Ni as NiO (%) 2.7 3.9 2.7 2.5 2.4 1.1 1.5
total Na as Na,O (%) 34.8 34.4 33.1 39.2 32.6 37.8 33.0
total Ca as CaO (%) 1.7 1.9 2.5 1.7 3.1 1.6 1.7
total Mg as MgO (%) 0.6 0.6 0.8 0.6 0.6 0.6 1.8
VzO, + Na20 + SO3 (%) 83.5 85.0 82.4 92.0 83.3 91.8 83.4
Na,0/V,05 (mol ratio) 60.1 47.2 57.1 92.0 39.8 56.5 46.1
Na20/SO3(mol ratio) 0.74 0.92 0.90 0.98 0.86 0.90 0.89

* The deposit was collected from the tube where the corrosion data superimposed in Fig. 8 were obtained.

Table 4. Specification of boiler (Case 2) years' service. One 316 H test tube (No. 21) and one 347 H test
Tabelle 4. Daten des Kessels Nr. 2 tube (No. 20) were removed after 5.5 years' service. Heavy
and crude mixed oils with addition of sludge were fired during
Capacity: 1,750 t/h the tests in this boiler. The average composition of the
Steam pressure: 255 kglcm' impurities in the oils is shown in Table 5. It turns out that the
Steam temperature: 541 "C (outlet of superheater) mixed oil, due to its higher V, Na and S contents is more
541 "C (outlet of reheater)
Type: straight through boiler corrosive than the oil fired in Case 1 boiler. Moreover, the
mixed oil may be more corrosive by addition of sludge.
The cross-sections of test tubes after 3 and 5.5 years' service
347H were installed in the first row of the final stage super- are shown in Fig. 13. The corrosion is not uniform over the
heater shown in Fig. 12. The two 316 H test tubes installed as circumference of the tubes and is more severe at the rear side
No. 9 and 16 (from the right side wall) tubes and the two 347 H than at the flame side, as is clearly recognized from the results
tubes installed as No. 8 and 15 tubes were removed after 3 after 5.5 years' service.

S.E. -
20pm
Cr Ni

Fe Nb S

Fig. 9. Electron and X-ray images of scale on

plate superheater tube (PSH 1)
Abb. 9. Elektronen- und Rontgenbilder des
Zunders auf einem Rohr des Plattenuberhitzers
Na V Nr. 1
74 Kihara, Ohtomo, Kajigaya and Kishimoto Werkstoffe und Korrosion 39,69-83 (1988)

S.E. u Cr Ni
20 p m

Fe Nb S

Fig. 10. Electron and X-ray images of scale on

plate superheater tube (PSH 2)
Abb. 10. Elektronen- und Rontgenbilder des
Zunders auf einem Rohr des Plattenuberhitzers
No V Nr. 2

Cr Ni
SE. 20ym

Fe Nb S

Fig. 11. Electron and X-ray image of scale on

final stage superheater tube (FSH 1)
Abb. 11. Elektronen- und Rontgenbilder des
Zunders auf einem Rohr der Uberhitzerend-
Na V 0 stufe Nr. 1
Werkstoffe und Korrosion 39, 69-83 (1988) Recent plant experience 75

A carburized layer was always found on the surface in the 1982 ( 3 y e a r )

heavily corroded area of both 316H and 347H tubes (Fig. 14). 6.751 6.601
This finding implies that the tube was exposed to a low oxygen
potential atmosphere and the corrosion was related with
Na2S04 [12]. The maximum surface recessions of 316H and
347 H are shown in Fig. 15 as a function of exposure time. The
corrosion of 316 H is more severe than that of 347 H; this trend
becomes clearer after long time exposure. This might be attri-
buted to the instability of the scale on 316H (similar to 321 H).
It is concluded that the maximum corrosion rates of 316 H and
347H are 0.65 m d y e a r and 0.4 m d y e a r , respectively. The
corrosion rate of 347H in the Case 2 boiler is about 3 times
higher than that in the boiler of Case 1. This suggests that the 7.001 6.751
corrosion rate depends on the V, S and Na contents in the fuel
fired.

Table 5. Average impurity content of fuel fired in Case 2 boiler

TabeUe 5. Mittlerer Gehalt an Verunreinigungen im Brennstoff fur
den Kessel Nr. 2

v PPm Nappm S% ratio % L 1 1 . 7 0 4 1 1 4 . 7 0 2

heavy oil 23.3 14.4 2.36 38
crude oil 3.1 2.8 0.1 62 1984 (5.5 y e a r )
mixed oil 10.8 7.2 0.96
5.551

<

k 4 3 . 6 6 4 k b 3 . 5 9 4
e
Fig. 13. Cross-section of superheater tube after 3 and 5.5 years serv-
ice (Case 2)
Abb. 13. Schnitt durch ein Uberhitzerrohr nach 3 und 5,5 Betriebs-
jahren (Kessel Nr. 2)

I
I u
loou 1oou

FL 16003

FL 12 2 0 0

FL 8400

316H S S
-
25U 347H S S
- 2511

FL -/oO Fig. 14. Microstructures on scale/metal interface of severely corroded

tubes of 316H and 347H SS after 5.5 years service (Case 2)
Fig. 12. Boiler structure and location of tube tested (Case 2) Abb. 14. Mikrogefiige an der Zunder/Metall-Grenzflache von stark
Abb. 12. Kesselaufbau und Lage der untersuchten Rohrbereiche korrodierten Rohren aus den Stahlen 316H und 347H nach 5,5
(Kessel Nr. 2) Betriebsjahren (Kessel Nr. 2)
76 Kihara, Ohtomo, Kajigaya and Kishimoto Werkstoffe und Korrosion 39, 69-83 (1988)

- The chemical analysis of the deposits shown in Table 6 sug-

1
347H gests that the deposit was also more corrosive than that of
0
31 6H
-a-- Case 1 because of its higher V content.

Oil-fired plant (Case 3)

The surface recession of 2.25 Cr-1 Mo steel tubes in one year

in the superheater and reheater areas was measured between
5 the '82 and '83 inspections in the oil-fired boiler whose specifi-
cation is shown in Table 7. The boiler structure and internal
Time Xl0"hr diameter of the test sites are shown in Fig. 16, the impurity
contents in the oil fired in this test in Fig. 17. It is clearly seen
Fig. 15. Maximum surface recession of final stage superheater tubes that the oil is extremely corrosive because of the average V,
of 316 H and 347 H as a function of exposure time Na and S contents of 200 ppm, 40 ppm and 4.5%, respec-
Abb, 15. Maximale Wanddickenabnahme der Rohre aus den Stahlen tively.
316H und 347 H in der Uberhitzerendstufe in Abhangigkeit von der The tube wall thickness at 4 points on the circumference
Betriebsdauer were measured at each site. The results are shown in Fig. 18,
according to which there is a wide scatter from tube to tube. In
the reheater areas, there is a great difference in the average
Table 6. Chemical composition of deposit on superheater tube corrosion loss between the sites RH1 and RH2 (Fig. 19).
(Case 2) More severe corrosion occurred at RH 1 than in RH 2 which is
Tabelle 6. Chemische Zusammensetzung der Ablagerungen auf located in only 600 mm downstream of RH 1. This broad scat-
einem Uberhitzerrohr (Kessel Nr. 2) ter of corrosion data implies that the fireside corrosion is sensi-
tively affected by gas stream, compositions of gas and deposit,
total S as SO, (%) 37.4 volume of deposit formed, etc.
total Fe as Fez03 (%) 10.6 The average corrosion is shown additionally in Fig. 20
total V as V 2 0 5(%) 16.4 together with the gas and metal temperature diagram for the
total Ni as NiO (%) 5.2 test sites. Isocorrosion curves (indicated by dotted lines) can
total Na as Na,O (%) 25.6
be drawn. The corrosion rate of 2.25 Cr-1 Mo steel at the site
total Ca as CaO (%) 0.6
total Mg as MgO (%) 0.3 PSH 1 is estimated at about 0.4 mm/year from the isocorrosion
VzOs + Na20 + SO3 (%) 79.4 curves, but the actual corrosion rate of 316H is about half of
Na20/V205(mol ratio) 4.5 that. This suggests that the corrosion resistance of 316H is
Na,O/SO, (mol ratio) 0.89 superior to that of 2.25 Cr-1 Mo steel.
Table 8 shows the chemical compositions of deposits taken
from the tubes at each site. Note that the V content is higher at
the higher gas temperature (upstream) side.
In this plant, fireside corrosion was also investigated in Unit
Table 7. Specification of boiler (Case 3) No. 2, next to Unit No. 1 mentioned above. The two units
Tabelle 7. Daten des Kessels Nr. 3 were quite identical in their structure and the fuel fired. But
the corrosion rate at the site PSH2 of Unit No. 2 was 0.1 mm/
Capacity: 475 t/h year, i.e. half of that at the same site of Unit Nor. 1. The
Steam pressure: 131 kg/cm2
Steam temperature: 541 "C (outlet of superheater)
chemical composition of the deposits collected at PSH2 of
541 "C (outlet of reheater) Unit No. 2 is also shown in Table 8. Unit No. 2 was estimated
Type: single drum, natural circulation to be in the lower sulfidizing potential range because the Na20/
SO3 ratio was lower. Moreover, less excess air was used in the

Table 8. Chemical composition of deposits on tubes tested (Case 3)

Tabelle 8. Chemische Zusammensetzung der Ablagerungen auf den Rohren (Kessel Nr. 3)

location PSH 1 PSH 2 FSH 1 FSH 2 RH 1 PSH 2

(unit 2)

pH (1 g/lOOml/H20) 4.6 3.8 3.4 3.4 2.8 -

total S as SO3(%) 34.8 27.0 14.8 16.5 18.1 43.5
total Fe as Fe203(%) 1.7 12.1 12.7 16.7 10.5 4.6
total V as V 2 0 5(%) 14.3 18.0 32.3 28.0 32.1 24.8
total Ni as NiO (%) 4.4 3.9 7.1 4.3 8.4 2.8
total Na as N a 2 0 (%) 27.1 20.0 9.9 12.7 8.7 21.2
total Ca as CaO (%) 0.2 0.3 0.3 0.3 0.3 0.1
total Mg as MgO (%) 2.7 2.7 3.9 3.0 4.9 4.5
V205+ NazO + SO, (%) 76.2 65.0 58.0 51.2 58.9 89.5
N a 2 0 N 2 0 5(mol ratio) 5.54 3.25 0.90 1.33 0.79 2.50
Na20/S0, (mol ratio) 1.01 0.96 0.90 1.00 0.62 0.63
Werkstoffe und Korrosion 39, 69-83 (1988) Recent plant experience 77

ID of locatmn

Steam pressure (kg/cm')

Number of tube tested
Tuba s m r b d Imm) 00 43 13 5
ID Of IDcatlO" Material 2.25Cr-1 Mo

Steam pre%PwC Ckgicm'

ID of location
Nnmber of tube tasted
Tubs smcifisd imm) OD38 1 T7 5
Material 2 25Cr-1Mo

ID of location

Steam pressure CkgilCm')

Number of tube tested
Tuba IW w c f i e d lmm) 0038 1 T4 5
Material 225Cr-1Mo

ID of location

S t e m Pressure (kglcm')
Number of tube tested
T u b sze smdcd (mml 0038 1 T8 5
Material 2.25Cr-1 MO

ID of IOC~UOII

Steam pressure ikg/cm')

Number Of tube tested
T u k we ~ p c m a d(mm) 0038 1 15 5
Material 31855

L-
Burner Fig. 16. Site at which the corrosion investigation was performed
(Case 3)
Abb. 16. Lage der fir Korrosionsversuche ausgewahlten Bereiche

--i Burner Burner (Kessel Nr. 3)

A
v 0.5

100-
E
8 80-

' 60 -
z:.
v

40- ._
20 -
-- 2 ... .. . .. . . .. . .
0.5-
. .
0 2
PSH 1 (316H

3.51 I

0 0 0

Nov Dec Jan Feb Mar Apr May Jun July Aug Sep
'82 '83 '1 5 10 15 20 25
Year
Tube number
Fig. 17. Change of impurity content of fuel burned in Case 3 boiler
(Unit 1 and 2) Fig. 18. Measured corrosion loss in superheater area (Case 3)
Abb. 17. Veranderungen im Gehalt an Verunreinigungen im Brenn- Abb. 18. Gemessene Korrosionsverluste im Uberhitzerbereich (Kes-
Kessel Nr. 3 (Einheit 1 und 2) sel Nr. 3)
78 Kihara, Ohtomo, Kajigaya and Kishimoto Werkstoffe und Korrosion 39,69-83 (1988)

Water wall tube (Case 4)

Location Ave. Corr. Rate
Heavy corrosion occurred in furnace water wall tubes of two
E RH 2 0.13 mm/year coal-fired boilers in which the same quality coal was fired.
E 0.5 The specification and the structure of the boiler in which
ai
t. 0.4 - 0 0 0 0 - fireside corrosion was investigated are shown in Table 9 and
I
0.3 - Fig. 21, respectively. Table 10 shows the characteristics of the
.-6
0 0
0
u)
2 0.2 - 0 0 0 0
coal.
The tube wall thickness was measured in a whole furnace
s 0
L

0.1 0 0
~

water wall area after 2 years' service. The measurement results

0 ' : : " ' * - g : = ' I ' obtained in the left side furnace wall at various elevations and
4 8 12 1 6 20 24 28 32 36 40 44 48 52
in the four sides at burner B level are shown in Fig. 22 and 23,
Tube numbei respectively. The side walls were heavily corroded at the
Fig. 19. Measured corrosion loss in reheater area (Case 3) burner 1evels.The maximum surface recession is estimated to
Abb. 19. Gemessene Korrosionsverluste im Uberhitzerbereich (Kes-
be about 3 mm.
sel Nr. 3) The chemical compositions of deposits on No. 28 and 49
(from the front wall) tubes of the left side wall are shown in
Table 11. The deposits mainly consist of iron sulfide and con-
tain almost no Na, K and C1. For the corrosion of furnace
water wall tubes, the corrosion by molten pyrosulfates
600 FSH 2 (Na2S207,KzS2O7)and by HCl are well known [13, 141. How-
ever, judging from the chemical composition of the deposit,
u @-- the corrosion in this boiler cannot be explained by the above
-
a
2

2
mechanisms. The results of DTA (differential thermal analy-
sis) and T G (thermogravimetry) measurements show that the
550- deposit contains FeS, but no alkali sulfates (Fig. 24). The elec-
E
z- Corrosion rate
tron and X-ray images of deposit and scale in Fig. 25 confirms
c
m
(mm/year)
that the main component of the deposit is iron sulfide.
i Pyrite (FeS2) contained in coal is converted into SO2 in the
combustion zone. However, pyrite melts and then deposits on
500;
I furnace water wall tubes as Fe2S or FeS in the locally reducing
4 I I 1 I I
atmosphere. FeSz corrodes metal (Fe) and forms FeS by the
900 1000 1100 1200
Gas temperature 'C following equation:

Fig. 20. Effect of gas and metal temperatures on corrosion rate of FeS2 + FeS + S(g)
2.25 Cr-1 Mo steel tube in superheater area (Case 3) S(g) + Fe (tube metal) + FeS
Abb. 20. EinfluR der Gas- und der Metalltemperatur auf die Kor-
rosionsgeschwindigkeit von Rohren aus 2,25 Cr 1Mo-Stahl irn Reducing atmospheres could form easily in the furnace side
Uberhitzerbereich (Kessel Nr. 3) wall area, because the boiler was operated with two stage
combustion to reduce NOx, so that hydrogen, hydrocarbon,
carbon monoxide and hydrogen sulfide gases were possibly
involved in the reducing atmosphere. Therefore, sulfidation
fire box of Unit No. 2 than in Unit No. 1. Therefore, the can also occur under conditions of SOzand C O co-existence by
difference in the corrosion rates between Units No. 1 and the following equations:
No. 2 can be attributed to the difference in the excess air. The
existence of Fe2S (detected in the scale on the superheater
3CO + SO2 + COS COZ +
tube of Unit No. 2) confirms that the atmosphere was in the COS + Fe + FeS CO +
low oxygen potential range. or
In Unit No. 1 corrosion tests using an air-cooled test probe
were performed for 2 years to evaluate several steels. The test 2CO + SO, + Fe + FeS + 2 C 0 2
results show that the corrosion rate of 9 Cr-1 Mo steel is about
a quarter of that of 2.25 Cr-1 Mo steel and equivalent to that of
7 CO + 2 SOz + Fe203-+ FeS + 7 C 0 2
347 H. The above corrosion mechanisms suggest that the corrosion
in this unit was possibly caused by the FeS deposit or the CO-
SO2 atmosphere.
Coal-fired boiler

Since low corrosive coals like an Australian coal have been Table 9. Specification of boiler (Case 4)
widely used in Japan, although some erosion problems have Tabelle 9. Daten des Kessels Nr. 4
been reported, fireside corrosion has seldom occurred in
superheater and reheater areas of coal-fired boilers in Japan. Capacity: 550 tlh
On the other hand, corrosion in reducing atmosphere has Steam pressure: 173.5 kglcm'
Steam temperature: 569C (outlet of superheater)
occurred in the furnace water wall area when two stage (sub- 541 "C (outlet of reheater)
stoichiometric) combustion was introduced for suppressing Type: single drum, natural circulation)
NOx.
Werkstoffe und Korrosion 39,69-83 (1988) Recent plant experience 79

-
2o B u r n e r D

. 1 9 -
:
I

5 18-
BurnerA E
L -
E
vi
w 'J-
(il
m Y
C
E 0
12 16- 5

,3
1-
BurnerC 2

25 50 75
Tube Number from Front of Furnace

Fig. 22. Measured tube wall thickness at various elevations of left side
water wall
Abb. 22. Gemessene Rohrwanddicken in verschiedenen Hohen der
linken Wasserwand

Tube number 6

--
a m
I-?

Fig. 21. Boiler structure in which the corrosion of water wall tube was Front 3.5
investigated Fig. 23. Measured tube wall thickness in four walls at Burner B level
Abb. 21. Kessel, in dem die Korrosion der Wasserwandrohre unter- Abb. 23. Gemessene Rohnvanddicke an vier Wanden in der Hohe
sucht wurde des Brenners B

Therefore, laboratory corrosion tests under simulated
atmospheres were carried out to clarify the corrosion mechan-
ism. In the first test, test coupons coated with FeS powder
were exposed to reducing and oxidizing atmospheres at 500 "C.
The test results showed that the corrosion is accelerated by
FeS in both reducing and oxidizing atmospheres (Fig. 26). In
the other test, test coupons were exposed to a flowing gas
containing CO and SO*. As shown in Fig. 27 it could be con-
firmed that SO2 addition to a reducing atmosphere (CO +
C02) accelerates the corrosion.

Table 10. Coal and ash charakteristics (Case 4)

Tabelle 10. Eigenschaften der Kohle und der Asche (Kessel Nr. 4)

approximate analysis (%) ultimate analysis (%) ash fusion temperature ("C) ash composition (%)
reducing atmosphere

inherent moisture 1.6 carbon 54.3 initial def. 1170 SiOz 51.5
fixed carbon 33.3 hydrogen 4.0 softening 1200 '41203 23.6
volatile matter 33.5 nitrogen 8.0 hemisphere 1240 Fe203 8.23
ash 31.6 oxygen 6.1 fluid 1340 Ti02 1.96
sulfur 3.2 CaO 9.82
MgO 1.57
NazO 2.34
KzO 1.18
so3 2.87
80 Kihara, Ohtomo, Kajigaya and Kishimoto Werkstoffe und Korrosion 39,69-83 (1988)

Table 11. Characteristics of deposit (Case 4)

Tabelle 11. Eigenschaften der Ablagerungen (Kessel Nr. 4)
Tube No. No. 28 No. 49

chemical composition (%)

Si02 3.30 4.07
A1203 1.62 1.70
Fe203 19.6 15.4
CaO 0.40 0.50 Na

MgO 0.07 0.09

Na20 0.12 0.16
K20 0.09 0.10
Ti0 0.07 0.08
so3 2.48 2.49
FeS 68.7 70.8

ash fusion temperature rC)

initial def. 1100 1130
softening 1260 1240 te 5
hemisphere 1320 1305
fluid 1340 1335

Research
Coal-ash corrosion

A laboratory corrosion test and a probe test in an actual C CI

coal-fired boiler were made by the authors [l-31 to clarify the
corrosion mechanism and to evaluate the corrosion resistance
of commerical alloys in the coal combustion atmosphere of an
ultra supercritical unit.
A picture and illustration of scale and deposit formed on the
17-14CuMo steel probe are shown in Fig. 28 [2]. The scale
and deposit consist of five different layers having the chemical

0 K
In Nitrogen
Fig. 25. Electron and X-ray images of scale and deposit on furnace
67.5- water wall tube of carbon steel
FeSz-FeS+S 87.5
Abb. 25. Elektronen- und Rontgenbild des Zunders und der Ablage-

550b
s rungen an einem Wasserwandrohr aus Kohlenstoffstahl
750
t-
0

42 5 62 5
62.5
compositions shown in Table 12 [ 2 ] .The main corrosion prod-
uct was iron oxide (layer 3) formed above the internal Cr sul-
1 Y l fide and oxide (layer 1 and 2 ) . Alkali sulfates were contained
30 00
3001 , 2 0 , 0 0 , 4000
, 1 50 0
, 6 0,0 0 , 8 0,0 0 , 10000
00 2 0 0 0 4000 6 0 0 0 8 0 0 0 10000 in these porous scales. Based on these results the authors ex-
Temperature -C plain the coal-ash corrosion mechanism in terms of the
sequence illustrated in Fig. 29 [ 2 ] . It was concluded that the
I-
4500 In Air

325.01 n, 92.5
corrosion was a catastrophic oxidation and can be explained by
the acidic-basic fluxing model mediated by molten alkali iron
sulfate.
Consequently, it was clarified that the potential for coal-ash
corrosion can be expressed as a function of temperature, SO2
content in the flue gas and alkali sulfate content in the ash.
However, the dependence on each parameter varies with the
material. Therefore, isocorrosion diagrams as functions of SO2
- 50 0 and alkali sulfate contents at various temperatures and for
00 2000 4000 6 0 0 0 8 0 0 0 10000 various material types are useful for obtaining the corrosion
Temperature C
rates to be expected in practice. In the task group for coal-ash
Fig. 24. Thermogravimetry (TG) and differential thermal analysis corrosion of the EPRI Research Project Boiler R&D for
(DTA) of deposit on water wall tube improved coal-fired plants, isocorrosion diagrams for more
Abb. 24. Thermogravimetrie und Differentialthermoanalyse der than 20 candidate materials are being set up by the authors.
Ablagerungen auf einem Wasserwandrohr An example of such an isocorrosion diagram is shown in
Werkstoffe und Korrosion 39, 69-83 (1988) Recent plant experience 81

Table 12. Summary of scale and deposit analysis on test probe

Tabelle 12. Ubersicht der Analyse von Zunder und Ablagerung auf
der Priifsonde
@&m
Without Fes} In 60% C O , 40% CO. ~

E 3 3 With Fes
designation elements detected remarks
~ ~ ~

30 - layer I Cr, Fe, Ni, Mo, 0, S, K Cr sulfide predominant

Mo concentrated
K penetrated between
-:
m
scale lamellas
E layer I1 Cr, Ni, Fe, 0, Mo, S Cr oxide predominant
(Mo and S exist only in the Ni sulfide formed at the
interface of layer I) interface of layer I
layer I11 Fe, 0, K, Ni, S, A1 Fe oxide predominant
layer IV Ca, Fe, Mg, Al, Si, K, 0, S Ca sulfate predominant
layer V Fe, Al, Si, Ca, Mg, K, 0, S Fe, A1 and Si oxides
predominant

Fig. 30 [4]. Note that the isocorrosion curves satisfactorily

2.25Cr-1Mo
Fig. 26. Effect of FeS deposit on the corrosion of carbon and 2.25 Cr-
1Mo steels in oxidizing and reducing atmospheres
Abb. 26. EinfluR von FeS-Ablagerungen auf die Korrosion von Koh-
lenstoffstahl und 2,25 Cr l Mo-Stahl in oxidierender und reduzieren-
der Atmosphare
coincide with the results of probe tests in an actual boiler.
The comparison of the corrosion resistance of 12 commer-
cial alloys under conditions simulating a high sulfur coal com-
bustion atmosphere is shown in Fig. 31 [4]. It suggests that the
alloys containing over 25% Cr show satisfactory corrosion re-
sistance.
EPDC (Electric Power Development Co., Ltd.) is conduct-
ing a series of field tests of boiler elements in two actual coal-
fired boilers [15]. Useful information for various types of
materials are expected to be obtained from the field tests, i.e.
industrial operation at 595 and 650 "C.

Development of materials technology

Composite tubes

Since the advanced steam cycle (ASC) boilers are operated

Fig. 27. Effect of SO, on the corrosion of carbon and 2.25 Cr-1 Mo
steels in CO-CO, atmosphere
Abb. 27. EinfluR von SO, auf die Korrosion von Kohlenstoffstahl und
2,25 Cr 1Mo-Stahl in CO-C02-Atmosphare
Fig. 28. Profile of scale and deposit formed on the test probe after
6,000 hrs' exposure
Abb. 28. Profil vom Zunder und Ablagerung auf der Priifsonde nach
6000 h
at higher temperatures and pressures than conventional boil-
ers, higher creep strength is required for superheater and re-
heater tube materials. Furthermore, in coal-fired ASC boilers,
a high resistance to coal-ash corrosion is needed. But creep
strength and corrosion resistance are generally incompatible.
Therefore, composite tubes, like co-extruded and coated
tubes, are technically and economically promising. It0 et al.
[lo] reported the results of an extensive programme covering
metallurgical , parameters, mechanical properties, creep
strength, corrosion and fabrication, using-extruded and diffu-
sion coated tubes. In this study 17-14CuMo, fine-grained
TP347H, Tempaloy A-1, Alloy 800 H and conventional
TP 347 H were selected as inner tube materials, and 310 SS,
35Cr-45Ni steel and chromizing were selected as the outer,
corrosion-resistant layers of the composite tubes. The results
demonstrated that
- co-extruded tubes and chromized tubes can be produced by
normal manufacturing procedures without affecting the
strength of the tubes,
- the tubes may be designed by assuming that only the inner
tube is pressurized,
- resistance to coal ash corrosion is greatly improved by both
cladding and chromizing,
- the cladding(coating)/tube interface is stable in service,
- welding and bending composite tubes can be accomplished
with no significant difficulty.
82 Kihara, Ohtomo, Kajigaya and Kishirnoto Werkstoffe und Korrosion 39, 69-83 (1988)

............. Na2SOq + K$04 Fe, Cr, Ni

sulfides
Note q@g@Molten -
sulfatea l k a l i iron ;-,!%% Precipitation of
nmmmmmn Cr rich oxide -Fe and Ni oxides
aJ
u,

0
.:.: . -.-, -
;*:
--
a,
t.

.*
c
0 1;0
.d

.-
(51
Metal u
0
I Metal
Metal

Step I Step I 1 Step I I I Step iv Step V

1s cmerted F a m t i m of mlta Irward sulfichtim Crock and exfoliation After repxition
into So, alkoli irm Md oxlchtion, of scale, of Stm 111 and I V
cntolvze of Fe2q Sulfate Fe, Ni,ond To Penetraticn of mlten
f o m m lretal flux into miten sult into the cracked
surface alkoli ircn scale Fig. 29. Schematic illustration of coal-ash cor-
sulfate Dissolution of sulfides
Precipitation of in mlten salt rosion sequence
fe and Ni oxides Abb. 29. Schema des Korrosionsablaufs bei
at the melt surface . Einwirkung von Kohlenasche

New alEoys
17-14CuMo ~(N&0,+KiSO1) and SO2 content range
I
650'C Open Symbols Eased on coal ash composition New alloys possessing high creep strength and corrosion
-z
~ Closed Symbols Eased on acidsoluble(Na+K)
content o f deposit on tube surface
resistance have been developed for use as a mono-wall tube.
The following four alloys are promising: 23 Cr-34 Ni -1.25 Mo-
c

0.4Ng (Mod. Alloy 800 H) [ 5 ] , 30 Cr-50Ni-2Mo-0.2Ti-0.02 Zr

(CR30 A) [7, 91, 25 Cr-20Ni-Nb-N (HR3C) [6], 20Cr-25-Ni-
1.5Mo-0.25Nb-0.05Ti-0.15N (NF709) [8]. It has been con-
firmed that the boiler tubes of these alloys can be manufac-
tured by existing procedures. Moreover, judging from the Cr
contents of these alloys, satisfactory resistances to coal-ash
corrosion can be anticipated.

Conclusion

Fireside corrosion accompanied by sulfidation is predomi-

nant in recent oil-fired boilers when low V oil and low excess
air combustion are used. However, in spite of the use of low
vanadium oil, the fireside corrosion has not been perfectly
suppressed. For example, the corrosion rates of 347H in the

30 Temperature : 650C 3
Ash : K 2 S 0 4 + N a 2 S 0 45%
N Atmosphere : 0.25%S02 x
.M5-.
1
Time : lOOh E
E
E 20
u)
0
-I
r'
.-'00
s
1
lo
Fig. 31. Comparison of the corro-
sion resistance of commercial alloys
in coal-combustion atmospheres
Abb. 31. Vergleich der Korrosions-
bestandigkeit handelsiiblicher Legie-
rungen in den bei der Kohleverbren-
Alloys nung entstehenden Atmospharen
Werkstoffeund Korrosion 39, 69-83 (1988)
units firing oil with 0.24% S and 4 ppm V (Case 1) and
0.96% S and 10.8 ppm V were 0.08 mdyear and 0.4 m d
year, respectively.
Moreover, the application of two stage combustion for low
NOx operation gives rise to a new type of damage, i.e. corro-
sion of the furnace water wall tube of coal-fired boilers in
reducing atmosphere.
As to countermeasures to suppress the above corrosion
problems, the usefulness of a newly studied coloured fuel addi-
tive [17] and the increased reliability of the evaluation of local
corrosion by &probabilisticapproach [18] have been reported.
Furthermore, co-extruded tubes, chromized tubes and newly
developed alloys may be candidates resisting the various kinds
of corrosion mentioned above. Therefore, it appears desirable
to collect test results with these new materials in actual boilers.
References
(11 A. Ohtomo et al.: IHI Engineering Review, Vol. 16 (1983) 310.
[2] S. Kihura et al.: High Temperature Corrosion in Energy Sys-
tem, TMS/AIME, M. F. Rothmun (ed.) (1984) 361.
[3] K. Nukaguwu et al.: ASME JPGC-Pwr-38, 1983.
[4] W. Wolowodiuk et al.: 1st International Conference on
Improved Coal-Fired Power Plant, Proceedings, Nov., 1986.
Recent plant experience 83
[5] K . Tumuru et al., ibid.
[6] K. Yoshikawu et al., ibid.
[7] K. Kubo et al., ibid.
[8] H. Masumoto et al., ibid.
[9] M. Tumuru et al.; 1985 Exposition and Symposium on Industrial
Heat Exchanger Technology, Pittsburgh, Pennsylvania, Nov.,
1985.
[lo] M. Itoh et al., ASME 86-JPGC-FACT-8, 1986.
[ll] H. Fujikuwa et al.: The Thermal and Nuclear Power, Vol. 33
(1982) 611.
[12] K. Fukahori et al.: ibid., Vol. 28 (1977) 639.
[13] D. J . Lees and M . E. Whitehead, Corrosion Resistant Materials
for Coal Conversion Systems, D. B. Meudowcroft and M. I.
Manning (ed.), Applied Science Publishers, London (1983) 63.
[14] S. Brooks and D. B. Meudowcroft: ibid, 105.
[151 Y. Nukubuyashi: 1st International Conference on Improved
Coal-Fired Power Plant, Proceedings, Nov., 1986.
[16] Y. Nukubuyashi et al.: Coatings and Bimetallics for Aggressive
Environments, ASM, R. D.Sisson Jr. (ed.) (1984) 103.
[17] K . Fukuhori et al: The Thermal and Nuclear Power, Vol. 36
(1985) 125.
[18] Y. Fukudu et al.: Proceedings of No. 58 JSCE (Japan Society of
Corrosion Engineers) Symposium (1984) 24.
(Received: 04.09.1987) W 2543