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COORAL – MINIRISKFederal Instutute for Materials Research and Testing
Corrosion Aspects of Materials Selection for
CO2 Transport and Storage
Dirk Bettge, A.S. Ruhl, R. Bäßler, O. Yevtushenko, A. Kranzmann
Federal Instutute for Materials Research and Testing
Berlin, Germany
Also with the BAM COORAL-Team:T. Bohlmann, S. Bohraus, A. Göbel, P. Wichmann, E. Hoffmann
Bettge/Bäßler/Kranzmann ICEPE 20.6.2011 Folie 1
COORAL – MINIRISK
Contents
• COORAL Joint Research Project• COORAL Joint Research Project• Materials and Gas Selection
E i t d CO t• Experiments under CO2 stream• EC Experiments under Aquifer and CO2
• Conclusions• Outlook
Bettge/Bäßler/Kranzmann Folie 2ICEPE 20.6.2011
COORAL – MINIRISK
COORAL Main Goals• COORAL: CO2 Purity for Sequestraion and Storing
(CO2-Reinheit für Abscheidung und Lagerung)(CO2-Reinheit für Abscheidung und Lagerung)
• Funding by
– German Ministry of Economics (50 %)
– E.ON, Vattenfall, ENBW, VNG, Alstom (50 %)
• Scheduled term 42 months, start date 01.04.2009
• Objectives:
– Limits of impurities
CO– Developing phases in the CO2 stream
– Corrosion of compressor and tube materials
Geochemical reactions– Geochemical reactions
– Safety issues
– Cost effectiveness
Bettge/Bäßler/Kranzmann Folie 3
Cost effectiveness
ICEPE 20.6.2011
COORAL – MINIRISK
CCS Transport Chain
• BAM Fields of Interest:• BAM Fields of Interest:– Compression– Transport– Injection
T = 170 °C
T = 5 °C
Generation Compression InjectionTransport
Bettge/Bäßler/Kranzmann ICEPE 20.6.2011 Folie 4Storage T = 60 °C
COORAL – MINIRISK
Materials Selection
N b N Sh Si TNumber Name Short Sign Treatment1.4006 X12Cr13 KM
1.4313 X3CrNiMo13-4 KR QT650
essi
on
T 170 °C1.4542 X5CrNiCuNb16-4 KS P930
1.4562 X1NiCrMoCu32-28-7 KU
3.7165 Ti-Al6-V4 KXCom
pre T = 170 °C
1.1018 Soft Iron TA
1.0484 L290NB TB
1.0582 L360NB TC
rans
port
T = 5 °C1.8977 L485MB TD
1.7225 42CrMo4 IH
1.4021 X20Cr13 IN
onT
1.4034 X46Cr13 IO
1.4542 X5CrNiCuNb16-4 IS P930
1.4162 X2CrMnNiN22-5-2 IT
1 4562 X1NiC M C 32 28 7 IU
Inje
ctio
T = 60 °C
Bettge/Bäßler/Kranzmann Folie 5ICEPE 20.6.2011
1.4562 X1NiCrMoCu32-28-7 IU
COORAL – MINIRISK
Gas Selection
OxyfuelEstimated CO2 stream compositions
CO2 O2 N2 Ar NOx SOx H2O++ 99,95% 0,01% 0,01% 0,01% 50 ppm 50 ppm 0,01%+ 98,00% 0,67% 0,71% 0,59% 0,01% 0,01% 0,01%- 96,00% 1,34% 1,38% 1,25% 0,01% 0,01% 0,01%
85 00% 4 70% 5 80% 4 57% 0 01% 0 01% 0 01%
Oxyfuel
CO2 O2 N2 NOx SOx H2O Amin+ 99,80% 0,02% 0,02% 0,02% 0,02% 0,02% 0,02%
99 40% 0 01% 0 01% 0 01% 0 01% 0 01% 0 01%
Post-Combustion
-- 85,00% 4,70% 5,80% 4,57% 0,01% 0,01% 0,01%
- 99,40% 0,01% 0,01% 0,01% 0,01% 0,01% 0,01%
A. Kather, TUHH
So called „Worst Case Composition“ to start with:
CO2 – 2 % O2 – 750 ppm CO – 600 ppm H2O – 70 ppm SOx – 100 NOx2 2 pp pp 2 pp x x
Bettge/Bäßler/Kranzmann Folie 6ICEPE 20.6.2011
Variation of amounts of the impurities to determine their influence
COORAL – MINIRISK
Gas Reactions (without intermediates)
• SO2 + 7 H2O ⇒ H2SO4 (H2O)6 ; liquid sulphuric acid forms up to 120 °C
• CO + O2 ⇒ CO2 + 1/2O2 ; CO and O2 are consumed
• NO2 + CO ⇒ CO2 + 1/2N2 + 1/2O2; N2 is formed
• H2O + 2NO2 ⇒ HNO3 + HNO2, gaseous nitric acid and nitrous acid areformed to low amounts
• SO2 + 1/2O2 ⇒ SO3 ; is formed at > 60°C
Bettge/Bäßler/Kranzmann Folie 7ICEPE 20.6.2011
COORAL – MINIRISK
Screening Experiments under Ambient Pressure
3 Chamber Furnaces
Gas Mixing
Compression 170 °C
DataAkquisition
Bettge/Bäßler/Kranzmann Folie 8ICEPE 20.6.2011
COORAL – MINIRISK
Screening Experiments60 °C, 600 hours, 600 H2O – 70 SO2 – 100 NO2 – 750 CO – 8000 O2 (in ppm)
Bettge/Bäßler/Kranzmann Folie 9
42CrMo4 X2CrMnNiN22-5-2
ICEPE 20.6.2011
COORAL – MINIRISK
Screening Experiments5 °C, 600 hours, 600 H2O – 70 SO2 – 100 NO2 – 750 CO – 8.000 O2
• Very slight uniform corrosion of pipeline materials
Iron L290NB L360NB L485MB
Bettge/Bäßler/Kranzmann Folie 10ICEPE 20.6.2011
COORAL – MINIRISK
Phase Analysis Using XRD
- Amorphous or very fine grained layer
Bettge/Bäßler/Kranzmann Folie 11ICEPE 20.6.2011
COORAL – MINIRISK
Screening Experiments170 °C, 600 hours, 600 ppm H2O – 70 ppm SO2 – 100 ppm NO2 – 750 ppm CO –
8 000 ppm O8.000 ppm O2
Compressor materials
TiX12Cr131.4562 1 4313 1 4542 TiX12Cr131.4562 1.4313 1.4542
Bettge/Bäßler/Kranzmann Folie 12ICEPE 20.6.2011
COORAL – MINIRISK
Screening Experiments170 °C, 600 hours, 600 ppm H2O – 220 ppm SO2 – 1.000 ppm NO2 – 750 ppm CO
8 000 ppm O– 8.000 ppm O2
From here, the amount of impurities was increased beyond „worst case“
Ti 42CrMo41.4562 X12Cr13 1.45421.4313
Bettge/Bäßler/Kranzmann Folie 13ICEPE 20.6.2011
Pipeline steelsX20Cr13 X46Cr13 1.4162
COORAL – MINIRISK
60°C, 240 hours, 8.000 ppm H2O, 220 ppm SO2, 1.000 ppm NO2Amount of H2O was increased beyound “worst case”
Screening Experiments
Amount of H2O was increased beyound worst case
Pipeline steels X46Cr1342CrMo4
Bettge/Bäßler/Kranzmann Folie 14ICEPE 20.6.2011
Injection materials1.4562
COORAL – MINIRISK
Screening Experiments30°C, 120 hours, 8.000 ppm H2O, 220 ppm SO2, 1.000 ppm NO2
Pipeline steels X46Cr1342CrMo4
Bettge/Bäßler/Kranzmann Folie 15ICEPE 20.6.2011
X20Cr13 X12Cr131.45621.41621.4542 1.4313
COORAL – MINIRISK
Screening Experiments5°C, 8.000 ppm H2O, 220 ppm SO2, 1000 ppm NO2
A id d ti d t ditiAcid condensation under extreme conditions
Bettge/Bäßler/Kranzmann Folie 16ICEPE 20.6.2011
COORAL – MINIRISK
Screening Experiments5°C, 8.000 ppm H2O, 220 ppm SO2, 1000 ppm NO2
A id d ti d t ditiAcid condensation under extreme conditions
Pipeline steelsPipeline steels
Bettge/Bäßler/Kranzmann Folie 17ICEPE 20.6.2011
COORAL – MINIRISK
L290NB, Experiments over 120 h at 5°C
atio
n [p
pm]
Con
cent
ra
Bettge/Bäßler/Kranzmann Folie 18ICEPE 20.6.2011
COORAL – MINIRISK
Thickness Measurement L290NB5 °C, 2 % H2O, 650 ppm SO22 pp 2=> condensating acidapprox. 0.7 .. 1.0 mm loss/year
Bettge/Bäßler/Kranzmann Folie 19ICEPE 20.6.2011
COORAL – MINIRISK
Conclusions Screening ExperimentsPipeline Steels under Ambient Pressurep• At temperatures of 60°C and higher no corrosion observed under the
described conditions• At 30°C corrosion only under very high H2O content ≥ 8 000 ppm due toAt 30 C corrosion only under very high H2O content ≥ 8.000 ppm due to
acid condensation• At 5 °C corrosion only under high water content ≥ 2.000 ppm due to acid
condensationcondensation
Injection and Compression• „Compressor materials“ without corrosion• High alloyed „injection materials“ without corrosion• 42CrMo4 and X46Cr13 behave similar to pipeline steels42CrMo4 and X46Cr13 behave similar to pipeline steels
Bettge/Bäßler/Kranzmann Folie 20ICEPE 20.6.2011
COORAL – MINIRISK
C
Conditions:
Electro Chemical Experiments on Injection Materials
Conditions:
• Wet CO2 stream
• High temperature high pressure• High temperature, high pressure
• Aquifer water (“brine”) with high Cl- content
A if t i i th i li t th i j ti i t d i• Aquifer water can rise in the pipeline to the injection point during
the downtime
Bettge/Bäßler/Kranzmann Folie 21ICEPE 20.6.2011
COORAL – MINIRISK
Experimental
Chemical composition of the steels, %
C, max. Cr Mo Mn S, max. Ni Si, max. P, max. Cu N
1.4162 0.04 21-22 0.1-0.8 4-6 0.03 1.3-1.7 1 0.04 0.1-0.8 0.251.4021 0.25 12-14 1.5 0.015 1 0.04
1.7225 0.45 0.9-1.2 0.15-0.3 0.6-0.9 0.035 0.4 0.035
Simulation of the “real conditions” in the lab:
• Artificial brine similar to onshore CCS-site in Germany• Brine saturation with CO2• Continues CO2 flowContinues CO2 flow• Temperature 60 °C known as critical for CO2 corrosion
Bettge/Bäßler/Kranzmann Folie 22ICEPE 20.6.2011
COORAL – MINIRISK
Reference Temperature Brine composition
Experimental setup
electrodep
controllerBrine composition
Cations mg L-1 Anions mg L-1
Ca2+ 1760 Cl- 143300K+ 430 SO4
2- 3600
CO t
Mg2+ 1270 HCO3- 40
Na+ 90100
T 333 KCO2 in
CO2 out T = 333 KCO2 flow 3-5 L/hpH = 5.8-6.0
Counterelectrode
HeaterWE= test specimen
Bettge/Bäßler/Kranzmann Folie 23ICEPE 20.6.2011
COORAL – MINIRISK
Localized corrosionTheoretical background
CO2 corrosion:
H2O + CO2 + Fe = FeCO3 + H2
CO2 + H2O H2CO3
Anodic:Anodic:
Fe Fe++ + 2e-
Cathodic:
2HCO + 2 2CO 2 + H2HCO3- + 2e- 2CO3
2- + H2
2H+ + 2e- H2
Bettge/Bäßler/Kranzmann
Maurice V., Marcus P. in Modern Aspects of Electrochemistry, 2009
Folie 24ICEPE 20.6.2011
COORAL – MINIRISK
1 4021 (X20C 13) i CO2 t t d li b i80
90
1.4021X20Cr13
0.0
1.4021 (X20Cr13) in CO2 saturated saline brine
50
60
70
kΩ •
cm
2
X20Cr13
-0.5 g/Ag
Cl, V
20
30
40Rpo
l, k
-1.0
EAg
0 2 4 6 8 10 12 14 1610
20
t, days
Bettge/Bäßler/Kranzmann Folie 25ICEPE 20.6.2011
COORAL – MINIRISK
1 021 ( 20C 13) CO2
240
260
1.4021 (X20Cr13) in CO2 saturated saline brine
180
200
220
240
, µm
1.4021X20Cr13
120
140
160
180 P
it de
pth
-390 -380 -370 -360 -35080
100
120
-350 mV -400 mV-390 mVE applied, mV vs Ag/AgCl
-380 mV
Bettge/Bäßler/Kranzmann Folie 26ICEPE 20.6.2011
COORAL – MINIRISK
1 22 ( 2C ) CO2
600
1.7225 (42CrMo4) in CO2 saturated saline brine
160
-600
120
140
Ω •
cm
2
-620
AgC
l, m
V
100
R
pol, -640
E Ag
/A
0 2 4 6 8 10 12 14 16
80-660
Time, days
Corrosion rate 1 9
Bettge/Bäßler/Kranzmann
Corrosion rate 1.9 mm/a
Folie 27ICEPE 20.6.2011
COORAL – MINIRISK
1 22 ( 2C ) CO2O
1.7225 (42CrMo4) in CO2 saturated saline brine
FeFe
FeFe
O
FeFe
Bettge/Bäßler/Kranzmann
FeCrCr
Folie 28ICEPE 20.6.2011
COORAL – MINIRISK
1.4162 (X2CrMnNiN22-5-2) in CO2 saturated saline brine
220
X2CrMnNiN22-5-2 150
-100
200
210
cm2
-250
-200
-150
mV
180
190
R
pol, k
Ω •
c
-350
-300 E
Ag/
AgC
l, m
150
160
170
R
500
-450
-400
0 2 4 6 8 10 12 14 16150
Time, days
-500
Bettge/Bäßler/Kranzmann Folie 29ICEPE 20.6.2011
COORAL – MINIRISK
700
8001.4162 (X2CrMnNiN22-5-2) in CO2 saturated saline brine
400
500
600
h, µ
m
200
300
400
Pit
dept
h
150 V-190 -180 -170 -160 -150
0
100
E V-190 mV -150 mVE, VAg/AgCl-170 mV -160 mV
Bettge/Bäßler/Kranzmann Folie 30ICEPE 20.6.2011
COORAL – MINIRISK
C CConclusions EC Experiments
• In CO2 saturated saline brine material 1.4021 is not resistant to pittingcorrosion, 1.7225 shows uniform corrosion, alloy 1.4162 is resistant topitting corrosion
• Cl- ions concentration controlls the corrosion kinetics
Outlook
• Corrosion of piping steels in a circulating supercritical impure CO2environment
Bettge/Bäßler/Kranzmann Folie 31ICEPE 20.6.2011
COORAL – MINIRISK
Laminary Flow
Outlook: High Pressure Tests
Laminary Flow• Autoclaves with CO2 circuit, max. 120 bar, max. 200 °C• Installed, first experiments launched
Turbulent Flow• Max. 200 bar, 200 °C, Turbulent gas stream, max. 10 m/s, , g ,• Mechanical stress (ball on ring)• To be assembled
Bettge/Bäßler/Kranzmann Folie 32ICEPE 20.6.2011