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High temperature corrosion of candidate
materials for industrial boilers in biomass
combustion
Jiri Krejcik and Josef Cizner
16. February 2010, Oslo
SVÚM a.s.Research Centre Bechovice
190 11 Prague 9 CZECH REPUBLIC
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Corrosion test of candidate steels Corrosion test of candidate steels and alloys for biomass combustionand alloys for biomass combustion
a) Laboratory test in model environment (presented in the NGBW conference in Milan)
b) Field test on 5 different types of biomass combustion(co-combustion) boilers
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Type
Steam temperature [°C]
Pressure [bar]
Performance [t/h]
1 Biocel Paskov, CZ bark (wood chips) + coal + mine gas
grade-fired 486 83 50
2 Mondi Štětí, CZ bark + lignite
circumfluid 535 94 220
3 Växjö Energi AB, S wood chips + peat
circumfluid 535 100 90
4 TTS Třebíč, CZ straw
grade-fired water heating boiler 4
5 Dalkia Krnov, CZ lignite + wood chips (pollard - 2006)
lgnifluid 445 37,2 75
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Chemical composition [ %] Material Cr Ni Mo Mn Other
Low alloy steels 15Mo3 15 020
– – 0,30 0,52 C 0,16; Si 0,26
13CrMo4 4 15121
0,96 0,07 0,48 0,46 C 0,12; Si 0,21
10CrMo9 10 (T22) 15313
2,10 – 0,92 0,43 C 0,12; Si 0,22
T23 ▲ 2,3 – 0,15 0,27 C 0,06; Si 0,15; V 0,2; W 1,58; Nb 0,06; B 0,005; N 0,02; Al 0,02
T24 2,3 – 0,96 0,52 C 0,08; Si 0,3; P 0,005; S 0,001; Al 0,02; Al 0,02; N 0,007; V 0,23; B 0,0025; Ti 0,070
High alloy steels
T92 9,15 0,26 0,50 0,46 W 1,7;Si 0,22; Nb 0,6; N 0,05; V 0,2; B 0,003; C 0,11
X20CrMoV12 1 10,45 0,70 0,88 0,60 C 0,18; Si 0,22; V 0,26 Esshete 1250 14,90 9,65 0,94 6,25 C 0,084; Si 0,58; Nb 0,86; V 0,22; B 0,004 TP 347 H 17,60 10,70 – 1,84 Si 0,29; C 0,05, Nb 0,6 Ni-base alloys
SAN 28 * 27,00 31,00 3,50 2,0 C 0,02; Si 0,07; Cu 1,0
Alloy 625 * 22,00 Bal. 9,00 – Fe 3,0; Nb 3,5; C 0,025
* chemical composition range
boiler TTS Třebíč
▲ boiler TTS Třebíč, Växjö and Krnov
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Test samples - cuts of tubes from candidate materials fixed on the bar made from AISI 310 steel.
Uncooled samples were installed into boilers.
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Area: pulp and paper industryMoving - grate boilerPerformance: 50 t/hProduced steam: 486 °C/83 barFuel:bark (saw dust) + bark from deposit
(with earth) + coal - mine gas
Location of the test samples in boiler Paskov (CZ)
Time: 580 °C - 4 224 h, 7 032 h, 9 832 h640 °C - 4 224 h
coal-mine gas
natural gas SH1
SH2 LUVO1
LUVO2
ECO1
ECO2
DHD
bark
DMD
Electrofilter
airwatersteam
corrosion samplesgas temperature 580 °C
corrosion samplesgas temperature 640 °C
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samples 600 °C
Location of the test samples in boiler Štětí (CZ)
Area: pulp and paper industryCircumfluid – Foster WheelerPerformance: 220 t/hProduced steam: 535°C/94 barFuel:50 % bark + 50 % lignite
Time: 8 760 h, 17 520 h, 31 370 hTemperature: 600 °C
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Samples (SH1-SH2)Gas temperature 540°C
Samples (SH2-SH3)Gas temperature 580°C
Location of the test samples in boiler Växjö (S)
Area: heat and electricity generationBoiler: Sandvik IICircumfluidPerformance: 90 t/hProduced steam: 535 °C/100 barFuel:wood chips + peat
Time: 6 240 h, 15 000 h, 23 760 hTemperature: 540 °C and 580 °C
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samples 500 °C
Location of the test samples boiler Třebíč (CZ)
Area: heat generationBoiler: VESKO-SPerformance: 5 MWFuel: 100% wheat straw
Time: 2 000 h, 4 747 hTemperature: 500 °C
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Location of the test samples at the instalation of Krnov (CZ)
samples 450 °C
Area: heat and electricity generationIngnifluid - ČKD Dukla PraguePerformance: 75 t/hProduced steam: 445°C/37,2 barFuel:lignite + 20% pollard - 2006
lignite + wood chips - other years
Time: 1 560 h, 7 440 h, 9 456 h, 14 124 h, 21 647 h
Temperature: 450 °C
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Analysis of deposit
Deposit was taken from the location of samples
(scratched off from the surface of overheating tubes).
Analysis of elements was carried out by EMPA
analyzer, most important is the content of Cl
(chlorides) and S.
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1. Company: BIOCEL Paskov, CZBIOCEL Paskov, CZ
Analysis of deposit
Installation Mg Al Si Ca K Na Cl S O
2006 0,38 1,82 4,05 10,65 1,30 1,91 0,05 7,09 64,12
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2. Company: MONDI PACKAGING, Štětí, CZMONDI PACKAGING, Štětí, CZ
Analysis of deposit
Installation Mg Al Si Ca K Na Cl S O
2006 0,12 13,70 21,30 6,88 0,74 0,08 0,20 0,79 52,40 2007 1,04 16,18 8,84 28,80 0,80 0,60 0,12 7,01 25,11 2008 0,10 4,32 7,24 22,44 0,20 0,03 0,16 6,37 53,14 2009 0,17 8,36 9,24 17,33 0,71 0,15 0,22 1,60 59,74
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3. Company: VÄXJÖ Energi AB, SÄXJÖ Energi AB, S
Analysis of deposit
Installation Mg Al Si Ca K Na Cl S O
SH1 - SH2 3,94 5,71 12,15 19,64 4,02 0,79 0,33 9,12 33,01 2006
SH2 - SH3 2,46 1,38 5,32 12,30 15,27 1,20 0,12 5,64 47,87 SH1 - SH2 0,96 5,19 8,85 21,86 3,54 0,59 0,87 8,46 40,10
2007 SH2 - SH3 0,42 1,17 7,81 18,77 4,01 1,60 1,03 13,96 42,84 SH1 - SH2 0,48 0,77 1,58 8,47 1,29 0,30 1,47 0,87 39,75
2008 SH2 - SH3 0,63 0,82 1,80 13,12 2,53 0,59 0,88 1,25 27,03 SH1 - SH2 0,56 2,89 6,02 24,28 3,36 0,81 0,44 1,99 55,31
2009 SH2 - SH3 0,68 2,14 8,02 19,35 2,33 0,52 0,30 1,46 61,28
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4. Company: TTS, Třebíč, CZTTS, Třebíč, CZ
Analysis of deposit
Installation Mg Al Si Ca K Na Cl S O
2006 1,35 0,16 26,13 13,55 4,11 0,03 1,19 0,80 46,82 2007 0,32 1,79 20,36 13,29 1,52 0,04 1,38 0,63 57,23 2009 0,31 1,33 11,40 11,88 4,48 0,22 1,16 0,54 66,51
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5. Company: DALKIA Krnov, CZDALKIA Krnov, CZ
Analysis of deposit
Installation Mg Al Si Ca K Na Cl S O
2006 9,58 11,28 18,46 8,42 2,10 6,14 3,93 5,94 32,10 2007 0,14 8,88 6,53 8,43 1,04 0,36 0,03 0,25 68,77 2008 1,00 10,14 6,66 8,72 0,18 0,03 0,02 2,31 66,51 2009 0,04 8,68 5,60 11,22 1,42 0,38 0,17 2,89 67,20
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Evaluation
Weight changes of test samples were evaluated during the
down - time of boilers.
On diagrams are corrosion curves, corrosion rate is
depending on kind of biomass and temperature.
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PASKOV 640 °C/4224 h - metallography evaluation
0
0,5
1
1,5
2
2,5
3
3,5
4
4,5
10CrM
o9 10 T92
X20CrM
oV121
E1250
347H
SAN28 625
Tu
bes
th
ickn
ess
red
uct
ion
[m
m]
BIOCEL Paskov 580 °C
0
500
1 000
1 500
2 000
2 500
0 2000 4000 6000 8000 10000Time [h]
Wei
gh
t lo
ss
[g/m
2 ]
10CrMo9 1013CrMo4 415 Mo3T92X20CrMoV12 1E 1250347HSAN28625
Martensitic and austenitic steels have the equal corrosion resistance in both temperatures, corrosion resistance of low alloy steels is unacceptable.
The best corrosion resistance have Ni-base alloys
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High alloy martensitic and austenitic steels and Ni-base alloys havevery good corrosion resistance.
MONDI PACKAGING, Štětí - 600 °C
-500
0
500
1 000
1 500
2 000
2 500
3 000
3 500
4 000
4 500
0 5000 10000 15000 20000 25000 30000 35000
Time [h]
Wei
gh
t ch
ang
es [
g/m
2 ]
10CrMo9 1013CrMo4 415 Mo3T92X20CrMoV12 1E 1250347HSAN28625
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Växjö Energi AB - 580 °C
-300
300
900
1500
2100
2700
3300
0 5000 10000 15000 20000 25000
Time [h]
Wei
gh
t lo
ss [
g/m
2 ]
10CrMo9 1013CrMo4 415 Mo3T92X20CrMoV12 1E 1250347HSAN28625T23
Växjö Energi AB - 540 °C
-200
200
600
1000
1400
1800
2200
2600
3000
0 5000 10000 15000 20000 25000
Time [h]
Wei
gh
t lo
ss [
g/m
2 ]
10CrMo9 1013CrMo4 415 Mo3T92X20CrMoV12 1E 1250347HSAN28625T23
At temperature 540 °C - low alloy steels + martensitic steel T92 have very low corrosion resistance
At temperature 580 °C - corrosion resistance of low alloy + both martensitic steels is very low - the effect of Cl+S
The best – austenitic steels and Ni-base alloys
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0
50
100
150
200
250
g/m
2
K rnov – 450°C
15313 15121 15020 T 92X 20C rMoV12 1 E 1250 T P 347 H S AN28625 T 23
Třebíč 500 °C
0
500
1000
1500
2000
2500
0 1000 2000 3000 4000 5000
Time [h]
Wei
gh
t lo
ss [
g/m
2 ]
10CrMo9 1013CrMo4 415 Mo3T92X20CrMoV12 1E1250347HSAN28625T23T24
Only Ni-base alloys and austenitic steels have good corrosion resistance
Good corrosion resistance of all test materials - low temperature
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Evaluation of corrosion rateEvaluation of corrosion rate
Corrosion rate of low alloy steels has the linear character and the weight changes of samples are much higher as compared to other test materials (except of Dalkia Krnov) .
Austenitic steels and Ni-base alloys have the best corrosion resistance and the weight changes are very low in all cases.
The behaviour of martensitic steels is different and depends on the combustion atmosphere in boiler (deposit):
* In atmosphere with higher content of S (no Cl) - martensitic steels have very good corrosion resistance - similar to austenitic steels and Ni-base alloys (Biocel Paskov, Mondi Štětí).
* Different situation is in atmosphere with Cl (Třebíč) and Växjö (Cl + S), the corrosion resistance of martensitic steels is low and is similar to low alloy steels (except X20CrMoV12 1 at lower temperature 540 °C Växjö).
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Mechanism of corrosionMechanism of corrosion
EPMA microanalysis and metallography were used for the
study of corrosion mechanism.
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Fe O Cl S
60 36 2 1,75
Low alloy steelsLow alloy steelsEPMA microanalysis of corrosion layers
Inner corrosion layer [wt %]
Fe O Cr Cl S
50 38 7 0,3 0,4
Outer corrosion layer [wt %]
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Mechanism of initiation and growth Mechanism of initiation and growth ofof inner inner
oxidic layeroxidic layer
Initiation - attack of carbide particles distributed on grain
boundaries and equally distributed in matrix - transformation to oxides (with S, Cl) .
Documentation of this mechanism is shown on steel 10CrMo9 10
boiler Paskov (mainly sulphidation)
boiler Växjö (combination of S and Cl corrosion).
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Steel 10CrMo9 10 - Paskov
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Steel 10CrMo9 10 - Växjö
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Vz.è. A (15313,540) - z kor. vrs. do ZM
100.0100.0100.0100.0100.0100.0
000000
W%O
W%S
W%Cl
W%Cr
W%Fe
W%Mo
Pt Nº
10 20
100
80
60
40
20
0
[%]
corrosion layer
basicmaterial
(BM)
1 point - 10 µm
10CrMo9 10 - 540 °C - Växjö
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Vz.è. A (15313,540) - z kor. vrs. pøes penetraci do ZM
5.0005.0005.000
000
W%S
W%Cl
W%Cr
Pt Nº
1 10
5
4
3
2
1
05
corrosion layer penetration BM
1 point - 2 µm
10CrMo9 10 - 540 °C - Växjö
[%]
corrosion layer
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Fe O Cr Cl S
55 41 0,3 1,7 7,6
Martensitic steelsMartensitic steelsT 92, X20CrMoV12 1
Inner corrosion layer [wt %]
Fe O Cr W Cl S
30-50 35 20 0,9 0,2 7
Outer corrosion layer [wt %]
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Mechanism of growth Mechanism of growth of of inner corrosion inner corrosion
layerlayer
Penetration of O, S and Cl into basic material, prefentially carbide particles are attacked
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Växjö
Corrosion layer - thickness Penetration to BM
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X20CrMoV12 1 - Paskov
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Vz.è. T92 H
100.0100.0100.0100.0100.0100.0
000000
W%O
W%S
W%Cr
W%Fe
W%Mo
W%W
Pt Nº
10 20
100
80
60
40
20
[%]
1 point - 10 µm
T92 - Mondi
inner corrosion layer BM
1 point - 10 µm
outer corrosion layer
100
80
60
40
20
0
[%]
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Fe O Cr Cl S
59 37 0,5 2,0 1,5
Austenitic steelsAustenitic steels
Inner corrosion layer [wt %]
Fe O Cr Ni Mo Cl S
36 37 27 2,0 1,4 0,3 2,4
Outer corrosion layer [wt %]
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Mechanism of initiation and growth of Mechanism of initiation and growth of
inner corrosion layerinner corrosion layer
Initiation - attack of carbide particles and transformation to oxides.
Oxidation along austenitic grain boundaries.
Paskov 347H - 580 °C sulphidation
Växjö E1250 - 540 °C S and Cl corrosion
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Paskov - 347H
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Växjö
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Vz.è. E (E1250,540) - z kor. vrs. do ZM100.0100.0100.0100.0100.0100.0
000000
W%O
W%S
W%Cl
W%Cr
W%Fe
W%Mo
Pt Nº
10 20
Växjö - E1250 - 540 °C
1 point - 2 µm
100
80
60
40
20
0
[%]
penetration BM corrosion layer
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Vz.è. E (E1250,540) - z kor. vrs. pøes penetraci do ZM2.0002.000
00
W%S
W%Cl
Pt Nº
1 10
2
0
penetration BM
1 point - 2 µm
E1250- 540 °C - Växjö
%
corrosionlayer
1
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Ni-base alloysNi-base alloysSAN 28, 625
Alloys 625 - application for the atmosphere with Cl in waste incineration plants.Corrosion layers are very thin, much more thinner as compared to other test materials.
Mechanism of corrosionMechanism of corrosion
Observed only one very thin layer - up to 6 µm.
![Page 42: High temperature corrosion of candidate materials for industrial boilers in biomass combustion Jiri Krejcik and Josef Cizner 16. February 2010, Oslo SVÚM](https://reader036.vdocuments.us/reader036/viewer/2022062620/5519932555034653068b46f5/html5/thumbnails/42.jpg)
Inner corrosion layer [wt %]
Ni Cr O Mo Cl S
2,5-30 24-27 43 0,8-11 1,2 4,5
Penetration of O, S and Cl into basic material - attack of carbide particles and transformation into oxides (with S, Cl).
![Page 43: High temperature corrosion of candidate materials for industrial boilers in biomass combustion Jiri Krejcik and Josef Cizner 16. February 2010, Oslo SVÚM](https://reader036.vdocuments.us/reader036/viewer/2022062620/5519932555034653068b46f5/html5/thumbnails/43.jpg)
![Page 44: High temperature corrosion of candidate materials for industrial boilers in biomass combustion Jiri Krejcik and Josef Cizner 16. February 2010, Oslo SVÚM](https://reader036.vdocuments.us/reader036/viewer/2022062620/5519932555034653068b46f5/html5/thumbnails/44.jpg)
Växjö
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C O N C L U S I O N C O N C L U S I O N
Tests of candidate materials with uncooled samples from low alloy,
martensitic and A-steels and two Ni-base alloys show the effect of: corrosion atmosphere (content of sulphates, chlorides in deposit) temperature (temperature of combustion gases)
Metallographic analysis demonstrates the initiation of corrosion on
carbide particles and selective corrosion of the surface with corrosion
along grain boundaries in all test materials at higher temperatures (over
500°C). In corrosion products O, Cl and S were found, and penetration of
Cr, W, Mo, Ni from basic material was analysed (depending on chemical
composition of material)
Austenitic steels and Ni-base alloys have very good corrosion resistance
with thin corrosion layer. In low alloy steels and martensitic steels (except
of lower temperatures on Dalkia Krnov boiler) high corrosion rate with
thick corrosion layer was observed.
![Page 46: High temperature corrosion of candidate materials for industrial boilers in biomass combustion Jiri Krejcik and Josef Cizner 16. February 2010, Oslo SVÚM](https://reader036.vdocuments.us/reader036/viewer/2022062620/5519932555034653068b46f5/html5/thumbnails/46.jpg)
Thank you for your attention!