17.05h Bettge

Federal Instutute COORAL MINIRISK
for Materials Research and Testing
Corrosion Aspects of Materials Selection for CO2 Transport and Storage

Dirk Bettge, A.S. Ruhl, R. Bler, O. Yevtushenko, A. Kranzmann Federal Instutute for Materials Research and Testing Berlin, Germany
Also with the BAM COORAL-Team: T. Bohlmann, S. Bohraus, A. Gbel, P. Wichmann, E. Hoffmann
Bettge/Bler/Kranzmann
ICEPE 20.6.2011
Folie 1
COORAL MINIRISK
Contents
COORAL Joint Research Project Materials and Gas Selection Experiments E i t under d CO2 stream t EC Experiments under Aquifer and CO2 Conclusions Outlook
ICEPE 20.6.2011
Folie 2
COORAL MINIRISK
COORAL Main Goals

COORAL: CO2 Purity for Sequestraion and Storing
(CO2-Reinheit fr 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 Developing phases in the CO2 stream Corrosion of compressor and tube materials Geochemical reactions Safety issues Cost effectiveness
Bettge/Bler/Kranzmann ICEPE 20.6.2011 Folie 3
COORAL MINIRISK
CCS Transport Chain

BAM Fields of Interest: Compression Transport Injection
T = 170 C T = 5 C
Generation
Compression
Transport
Injection
ICEPE 20.6.2011
Storage
T = 60 C
Folie 4
COORAL MINIRISK
Materials Selection
N b Number
Transport Compre ession
1.4006 1.4313 1.4542 1.4562 3.7165 1.1018 1.0484 1.0582 1.8977 1.7225 1.4021 1.4034 1.4542 1.4162 1 4562 1.4562
N Name
X12Cr13 X3CrNiMo13-4 X5CrNiCuNb16-4 X1NiCrMoCu32-28-7 Ti-Al6-V4 Soft Iron L290NB L360NB L485MB 42CrMo4 X20Cr13 X46Cr13 X5CrNiCuNb16-4 X2CrMnNiN22-5-2 X1NiC M C 32 28 7 X1NiCrMoCu32-28-7
Sh Short Si Sign
KM KR KS KU KX TA TB TC TD IH IN IO IS IT IU
T Treatment
QT650 P930
T = 170 C
T = 5 C
Injectio on
P930
T = 60 C
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Folie 5
COORAL MINIRISK
Gas Selection
Estimated CO2 stream compositions
Oxyfuel
++ + -CO2 99,95% 98,00% 96,00% 85 00% 85,00%
CO2 99,80% 99 40% 99,40%
O2 0,01% 0,67% 1,34% 4 70% 4,70%

O2 0,02% 0 01% 0,01%
N2 0,01% 0,71% 1,38% 5 80% 5,80%

N2 0,02% 0 01% 0,01%
Ar 0,01% 0,59% 1,25% 4 57% 4,57%

NOx 0,02% 0 01% 0,01%
NOx 50 ppm 0,01% 0,01% 0 01% 0,01%

SOx 0,02% 0 01% 0,01%
SOx 50 ppm 0,01% 0,01% 0 01% 0,01%

H2O 0,02% 0 01% 0,01%
H2O 0,01% 0,01% 0,01% 0 01% 0,01%

Amin 0,02% 0 01% 0,01%
Post-Combustion
+ -
A. Kather, TUHH
So called Worst Case Composition to start with: CO2 2 % O2 750 pp ppm CO 600 pp ppm H2O 70 pp ppm SOx 100 NOx
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 are formed to low amounts SO2 + 1/2O2 SO3 ; is formed at > 60C
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Folie 7
COORAL MINIRISK
Screening Experiments under Ambient Pressure

3 Chamber Furnaces
Gas Mixing Compression 170 C
Data Akquisition
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Folie 8
COORAL MINIRISK
Screening Experiments
60 C, 600 hours, 600 H2O 70 SO2 100 NO2 750 CO 8000 O2 (in ppm)
42CrMo4
Bettge/Bler/Kranzmann ICEPE 20.6.2011
X2CrMnNiN22-5-2
Folie 9
COORAL MINIRISK
5 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
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Folie 10
COORAL MINIRISK
Phase Analysis Using XRD
- Amorphous or very fine grained layer
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Folie 11
COORAL MINIRISK
170 C, 600 hours, 600 ppm H2O 70 ppm SO2 100 ppm NO2 750 ppm CO 8 000 ppm O2 8.000
Compressor materials
1.4562
X12Cr13
1 4313 1.4313
1 4542 1.4542
Ti
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Folie 12
COORAL MINIRISK
170 C, 600 hours, 600 ppm H2O 220 ppm SO2 1.000 ppm NO2 750 ppm CO 8.000 8 000 ppm O2 From here, the amount of impurities was increased beyond worst case
1.4562
X12Cr13
1.4313
1.4542
Ti
42CrMo4
X20Cr13
X46Cr13
1.4162
ICEPE 20.6.2011
Pipeline steels
Folie 13
COORAL MINIRISK
60C, 240 hours, 8.000 ppm H2O, 220 ppm SO2, 1.000 ppm NO2 Amount of H2O was increased beyound worst worst case case
Pipeline steels
42CrMo4
X46Cr13
1.4562
Injection materials
ICEPE 20.6.2011 Folie 14
COORAL MINIRISK
30C, 120 hours, 8.000 ppm H2O, 220 ppm SO2, 1.000 ppm NO2
Pipeline steels
42CrMo4
X46Cr13
X20Cr13
1.4542
1.4162
1.4562
ICEPE 20.6.2011
X12Cr13
1.4313
Folie 15
COORAL MINIRISK
5C, 8.000 ppm H2O, 220 ppm SO2, 1000 ppm NO2 A id condensation Acid d ti under d extreme t conditions diti
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COORAL MINIRISK
5C, 8.000 ppm H2O, 220 ppm SO2, 1000 ppm NO2 A id condensation Acid d ti under d extreme t conditions diti
Pipeline steels
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Folie 17
COORAL MINIRISK
L290NB, Experiments over 120 h at 5C

Concentra ation [ppm]
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Folie 18
COORAL MINIRISK
Thickness Measurement L290NB

5 C, 2 % H2O, 650 pp ppm SO2 => condensating acid approx. 0.7 .. 1.0 mm loss/year
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Folie 19
COORAL MINIRISK
Conclusions Screening Experiments

Pipeline p Steels under Ambient Pressure At temperatures of 60C and higher no corrosion observed under the described conditions At 30 30C C corrosion only under very high H2O content 8 8.000 000 ppm due to acid condensation At 5 C corrosion only under high water content 2.000 ppm due to acid condensation Injection and Compression Compressor materials without corrosion High alloyed injection materials without corrosion 42CrMo4 and X46Cr13 behave similar to pipeline steels
ICEPE 20.6.2011
Folie 20
COORAL MINIRISK
Electro Chemical C Experiments on Injection Materials

Conditions: Wet CO2 stream High temperature, temperature high pressure Aquifer water (brine) with high Cl- content Aquifer A if water t can rise i i in th the pipeline i li t to th the i injection j ti point i td during i the downtime
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COORAL MINIRISK
Experimental
Chemical composition of the steels, % C, max. 1.4162 1.4021 1.7225 0.04 0.25 0.45 Cr 21-22 12-14 Mo 0.1-0.8 Mn 4-6 1.5 S, max. 0.03 0.015 0.035 Ni 1.3-1.7 Si, max. P, max. 1 1 0.4 0.04 0.04 0.035 Cu 0.1-0.8 N 0.25
0.9-1.2 0.15-0.3 0.6-0.9
Simulation of the real conditions in the lab: Artificial brine similar to onshore CCS-site in Germany Brine saturation with CO2 Continues CO2 flow Temperature 60 C known as critical for CO2 corrosion
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Folie 22
COORAL MINIRISK
Experimental setup
Reference electrode
Temperature p controller
Brine composition
Cations mg L-1 Anions mg L-1 Ca2+ 1760 Cl143300 K+ 430 SO423600 Mg2+ 1270 HCO340 Na+ 90100
CO2 out t CO2 in Counter electrode WE= test specimen
T = 333 K CO2 flow 3-5 L/h pH = 5.8-6.0
Heater
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COORAL MINIRISK
Theoretical background
Localized corrosion CO2 corrosion: H2O + CO2 + Fe = FeCO3 + H2 CO2 + H2O H2CO3 Anodic: Fe Fe++ + 2e-
Cathodic:
2 + H 2HCO3- + 2e 2 - 2CO322
2H+ + 2e- H2
Maurice V., Marcus P. in Modern Aspects of Electrochemistry, 2009
ICEPE 20.6.2011
Folie 24
COORAL MINIRISK
1 4021 (X20C 1.4021 (X20Cr13) 13) i in CO2 saturated t t d saline li b brine i

90 80 70
1.4021 X20Cr13
0.0
Rpol, k cm
50 40 30 20 10 0 2 4 6 8 10 12 14
-0.5
-1.0
16
t, days
ICEPE 20.6.2011
EAg ,V g/AgCl
60
Folie 25
COORAL MINIRISK
1 021 ( 1.4021 (X20Cr13) 20C 13) in CO2 saturated saline brine

260 240 220
1.4021 X20Cr13
Pit depth, m
200 180 160 140 120 100 80 -390 -380 -370 -360 -350
E applied, mV vs Ag/AgCl
-350 mV
-380 mV
-390 mV
-400 mV
ICEPE 20.6.2011
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COORAL MINIRISK
1 22 ( 1.7225 (42CrMo4) 2C ) in CO2 saturated saline brine

-600 600 160
140
2
-620
Rpol, cm
120 -640 100
80
-660
10
12
14
16
Time, days
Corrosion rate 1 1.9 9 mm/a

EAg/A , mV AgCl
COORAL MINIRISK
1 22 ( 1.7225 (42CrMo4) 2C ) in CO2 saturated saline brine

O
Fe
Fe Fe
Fe Cr Cr
Bettge/Bler/Kranzmann ICEPE 20.6.2011
Fe Fe
Folie 28
COORAL MINIRISK
1.4162 (X2CrMnNiN22-5-2) in CO2 saturated saline brine
-100 220 210 -200 200 190 180 170 160 150 0 2 4 6 8 10 12 14
X2CrMnNiN22-5-2
-150 150
Rpol, k c cm
-250 -300 -350 -400 -450 -500 500 16
Time, days
ICEPE 20.6.2011
EAg/AgCl, m mV
Folie 29
COORAL MINIRISK
1.4162 (X2CrMnNiN22-5-2) in CO2 saturated saline brine

800 700 600 500 400 300 200 100 0 -190 -180 -170 -160 -150
Pit depth h, m
-190 mV
-170 mV
E VAg/AgCl E,
-160 mV
150 mV V -150
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COORAL MINIRISK
C Conclusions EC C Experiments
In CO2 saturated saline brine material 1.4021 is not resistant to pitting corrosion, 1.7225 shows uniform corrosion, alloy 1.4162 is resistant to pitting corrosion Cl- ions concentration controlls the corrosion kinetics
Outlook
Corrosion of piping steels in a circulating supercritical impure CO2 environment
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Folie 31
COORAL MINIRISK
Outlook: High Pressure Tests

Laminary Flow Autoclaves with CO2 circuit, max. 120 bar, max. 200 C Installed, first experiments launched Turbulent Flow , 200 C, , Turbulent gas g stream, , max. 10 m/s Max. 200 bar, Mechanical stress (ball on ring) To be assembled
ICEPE 20.6.2011
Folie 32

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Federal Instutute COORAL MINIRISK

for Materials Research and Testing

Corrosion Aspects of Materials Selection for CO2 Transport and Storage

COORAL Main Goals

CCS Transport Chain

O2 0,01% 0,67% 1,34% 4 70% 4,70%

N2 0,01% 0,71% 1,38% 5 80% 5,80%

Ar 0,01% 0,59% 1,25% 4 57% 4,57%

NOx 50 ppm 0,01% 0,01% 0 01% 0,01%

SOx 50 ppm 0,01% 0,01% 0 01% 0,01%

H2O 0,01% 0,01% 0,01% 0 01% 0,01%

Variation of amounts of the impurities to determine their influence

Gas Reactions (without intermediates)

Screening Experiments under Ambient Pressure

Gas Mixing Compression 170 C

Phase Analysis Using XRD

- Amorphous or very fine grained layer

L290NB, Experiments over 120 h at 5C

Thickness Measurement L290NB

Conclusions Screening Experiments

Electro Chemical C Experiments on Injection Materials

0.9-1.2 0.15-0.3 0.6-0.9

CO2 out t CO2 in Counter electrode WE= test specimen

T = 333 K CO2 flow 3-5 L/h pH = 5.8-6.0

1 4021 (X20C 1.4021 (X20Cr13) 13) i in CO2 saturated t t d saline li b brine i

1 021 ( 1.4021 (X20Cr13) 20C 13) in CO2 saturated saline brine

1 22 ( 1.7225 (42CrMo4) 2C ) in CO2 saturated saline brine

120 -640 100

Corrosion rate 1 1.9 9 mm/a

1 22 ( 1.7225 (42CrMo4) 2C ) in CO2 saturated saline brine

1.4162 (X2CrMnNiN22-5-2) in CO2 saturated saline brine

-250 -300 -350 -400 -450 -500 500 16

1.4162 (X2CrMnNiN22-5-2) in CO2 saturated saline brine

Outlook: High Pressure Tests

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