Carburization and Oxidation of Power

Plant Steels under Oxyfuel-Conditions

Daniela Huenert, Wencke Schulz and Axel Kranzmann
BAM Federal Institute for Materials Research and Testing, Berlin, Germany

Modern CO2-reduced power plants with Oxyfuel-Combustion operate with gas compositions of high CO2 partial pressure and steam (Boiler, Recycling). The corrosion
process occurring under such service conditions is different from that under current conditions with air combustion. The effect of temperature, pressure, chromium
content on the corrosion reaction of typical power plant steels in CO2-H2O and CO2-H2O-O2 was investigated.

Experimental Oxidation
For experimental tests a pressure-oxidation-simulation-machinery for tubes H2O-CO2 H2O-CO2
was used. During the experimental procedure, an axial temperature gradient of
500-650 C was applied to the pressure loaded tubes, which causes a corrosion
process at the inner and the outer tube surface. The investigated steels differing
mainly in chromium content (Table 1). Corrosion tests were carried out in H2O-CO2

30 bar
1 bar
(30-70 mol %) and H2O-CO2-O2 (30-69-1 mol%) at a pressure of 1, 30 and 80 bar
for a time of 1000 h.

H2O-CO2 H2O-CO2-O2
80 bar

80 bar
2,4 9
% Cr

1 12

p, T

Carburization
1 12
H2O-CO2 H2O-CO2
% Cr
9
2,4
30 bar
1 bar

Analysis
On every oxidized samples, 800 individual measuring points with light microscopy H2O-CO2 H2O-CO2-O2
were summarized to give a good accuracy of scale thickness. The diffusion of
carbon was observed by a high resolution microprobe given carburization depths.

Table 1
80 bar
80 bar

Steel C Si Mn Al Cr Mo V Nb Ti W N Co
min 0,17 - 0,40 - 0,70 0,40 - - - - - -
13 Cr Mo44
max 0,19 0,35 0,70 0,04 1,15 0,60 - - - - - -
min 0,05 0,15 0,30 0,02 2,20 0,90 0,20 - 0,05 - 0,01 -
T24
max 0,10 0,45 0,70 0,02 2,60 1,10 0,30 - 0,10 - 0,01 -
min 0,07 - 0,30 - 8,50 0,30 0,15 0,04 - 1,50 0,03 -
P92
max 0,13 0,50 0,60 0,04 9,50 0,60 0,25 0,09 - 2,00 0,07 -
min 0,12 0,46 0,17 0,01 11,50 0,25 0,21 0,05 0,00 1,40 0,07 1,60
VM12 SHC
max 0,13 0,49 0,17 0,01 11,50 0,29 0,26 0,05 0,01 1,50 0,10 1,60

Comparison to corrosion in H2O Observations

! Scale thickness and carburization are increasing depending on temperature,
pressure, chromium content and the formation of protective FeCr2O4-Spinells:
! low alloyed steels show increasing scale thicknesses with increasing T, p
but the carburization decreases with increasing temperature
! 9-12 % Cr-Steels: As long a protective FeCr2O4-spinel has not been formed,
carburization rates and corrosion rates increases.
! Oxidation rates and carburization and rates are pressure dependent:

H2O (g) H2 (g)

CO2 (g,fl) CO (g)

0,75Fe " CO2 # 0,25 Fe3O4 " CO

Fe 3O 4
pores and channels
1,5Fe " CO2 # 0,5 Fe3O4 " C
Fe 3O 4 H2O (g)
0,75Fe " H 2O # 0,25Fe3O4 " H 2 + CO2 (g) H2 (g)
FeCr 2O 4 CO (g) 0,75Fe " CO # 0,25 Fe3O4 " C

FeCr 2O 4
+ aC 1 aC
Base material K% % $
pCO / CO2 p N CO / CO2
H2, C
2009-057a W

Acknowledgment: The authors acknowledge the financial support from the Federal Ministry of Economics and Technology, Germany
(Frdernummer/ Grat ID: 0327727B) ans the COORETEC program.