Kyra Campbell (Imperial College London) - Understanding and Addressing Corrosion Due to Amine Solvents in Post-Combustion Carbon Capture Processes - UKCCSRC Cranfield Biannual 21-22 April 2015

1. Understanding and addressing corrosion
due to amine solvents in post-combustion
carbon capture processes
KL Sedransk Campbell, DR Williams
Department of Chemical Engineering, Imperial College
UKCCSRC Biannual Meeting
April 21 2015

2. Outline
Background on corrosion, particularly in amine systems
Testing corrosion
1. Experimental methods and amines of interest
2. Analysis techniques
Corrosion observed for aqueous amine (binary) systems
1. Visual inspection and ‘hanging film’
2. Elemental analysis of the solution
3. Surface characterization and compositional analysis
Corrosion observed in aqueous amine (multi-component) systems
Conclusions

3. Background on Corrosion
Fe+2
2e-
ANODIC
H+OH- 2e-
H+
H2
CATHODIC
Fe + 2H+  Fe+2 + H2

4. Background on Corrosion
Fe+2
2e-
ANODIC
H+OH- 2e-
H+
H2
CATHODIC
Fe + 2H+  Fe+2 + H2
Fe(OH)2

5. Background on Corrosion
Fe+2
2e-
HCO3
-
H2
Fe + 2HCO3
-
 FeCO3 + CO3
-2
+ H2
FeCO3
HCO3
-
HCO3
-
2e-
2e-
Fe+2
Fe+2

6. Testing Corrosion
Experimental Methods:
1.Large scale (direct)
2.Electrochemistry
Fe+2
2e-
HCO3
-
H2
FeCO3
HCO3
-HCO3
-
2e-
2e-
Fe+2Fe+2
H2
H2

7. Testing Corrosion: Experimental Apparatus
Element Content %
Fe 98.851
C 00.170
Mn 00.800
Cr 00.040
Al 00.042

8. Testing Corrosion: Metal Coupons
Element %
Fe 98.851
C 00.170
Mn 00.800
Cr 00.040
Al 00.042
Typical Industrial Machine Finish

9. Testing Corrosion: Metal Coupons
Typical Industrial Machine Finish
120 Grit Testing Finish
Element %
Fe 98.851
C 00.170
Mn 00.800
Cr 00.040
Al 00.042

10. Testing Corrosion: Aqueous Amine Solutions
Monoethanolamine
(MEA)
#1: Primary
Methyldiethanolamine
(MDEA)
#1: Tertiary
Diethylenetriamine
(DETA)
#1, #2 Primary,
#3 Secondary
2-amino-2-methylpropanol
(AMP)
#1: Primary
1-(2-aminoethyl)-piperazine
(AEP)
#1: Primary,
#2: Secondary,
#3 Tertiary
Potassium Carbonate
(K2CO3)
N/A

11. Testing Corrosion
Analysis Methods:
1.Traditional: Hanging Film (Weight
loss/gain)
2.Bulk chemical (metal ions) contents:
ICP – OES
Fe+2
2e-
HCO3
-
H2
FeCO3
HCO3
-HCO3
-
2e-
2e-
Fe+2Fe+2
H2
H2

12. Testing Corrosion
Analysis Methods:
1.Traditional: Hanging Film
(Weight loss/gain)
2.Bulk chemical (metal ions) contents:
ICP – OES
3.Surface imaging: SEM, (AFM) Fe+2
2e-
HCO3
-
H2
FeCO3
HCO3
-HCO3
-
2e-
2e-
Fe+2Fe+2
H2
H2

13. Testing Corrosion
Analysis Methods:
1.Traditional: Hanging Film (Weight
loss/gain)
2.Bulk chemical (metal ions) contents:
ICP – OES
3.Surface imaging: SEM, (AFM)
4.Surface chemistry: EDX, (Raman)
Fe+2
2e-
HCO3
-
H2
FeCO3
HCO3
-HCO3
-
2e-
2e-
Fe+2Fe+2
H2
H2

14. Testing Corrosion
Analysis Methods:
1.Traditional: Hanging Film (Weight
loss/gain)
2.Bulk chemical (metal ions) contents:
ICP – OES
3.Surface imaging: SEM, (AFM)
4.Surface chemistry: EDX, (Raman)
5.Surface (crystal) structure: Visual,
SEM, XRD, (XPS)
Fe+2
2e-
HCO3
-
H2
FeCO3
HCO3
-HCO3
-
2e-
2e-
Fe+2Fe+2
H2
H2

15. CORROSION OF AMINES ON STEEL

16. Aqueous Amine Solutions – Visual Inspection
MDEA K2CO3 MEA AEP AMP
Corrosion: MEA, AEP, DETA Passivation: MDEA, AMP, K2CO3
DETA

17. -0.2
0
0.2
0.4
0.6
0.8
0 5 10 15 20 25 30
CorrosionRate(mmy-1)
Time (Days)
MEA
MDEA
AEP
AMP
K2CO3*
Aqueous Amine Solutions – Hanging Film Method
Corrosion Passivation
AEP MEA AMP MDEA K2CO3*

18. -0.2
0
0.2
0.4
0.6
0.8
0 5 10 15 20 25 30
CorrosionRate(mmy-1)
Time (Days)
MEA
DETA*
K2CO3*
Aqueous Amine Solutions – Hanging Film Method
Corrosion Passivation
AEP MEA DETA* AMP MDEA K2CO3*

19. Aqueous Amine Solutions – ICP - OES
0.1
1
10
0 5 10 15 20 25 30
[Fe](mgL-1)
Time (days)
MDEA
K2CO3*

20. Aqueous Amine Solutions – ICP - OES
0.1
1
10
100
0 5 10 15 20 25 30
[Fe](mgL-1)
Time (days)
MEA
MDEA
AMP
K2CO3*

21. 0.1
1
10
100
0 5 10 15 20 25 30
[Fe](mgL-1)
Time (days)
MEA
MDEA
AEP
AMP
K2CO3*
Aqueous Amine Solutions – ICP - OES
Corrosion Passivation
AEP MEA AMP MDEA K2CO3*

22. 0.1
1
10
100
0 5 10 15 20 25 30
[Fe](mgL-1)
Time (days)
MEA
DETA*
K2CO3*
Aqueous Amine Solutions – ICP - OES
Corrosion Passivation
AEP DETA* MEA AMP MDEA K2CO3*

23. Aqueous AMP Solutions – SEM / EDX
DAY 7 DAY 28

24. Aqueous AMP Solutions – SEM / EDX
DAY 7 DAY 28
100% Surface Coverage

25. Aqueous AMP Solutions – SEM / EDX
DAY 7
Passivation layer
Epoxy Resin
Steel Coupon

26. Aqueous AMP Solutions – SEM / EDX
DAY 7
Epoxy Resin
Steel Coupon
Oxygen
Iron

27. Aqueous AMP Solutions – SEM / EDX
DAY 14 DAY 28
Passivation Layer ~ 10µm Passivation Layer ~ 20µm
Epoxy ResinEpoxy Resin
Steel Coupon Steel Coupon

28. Aqueous K2CO3 Solutions – SEM / EDX
DAY 7
<100% Surface Coverage
Element Mole Ratio
C 14.86
O 5.15
Fe 79.99
Element Mole Ratio
C 18.12
O 51.36
Fe 30.52
Mixture of products?

29. Aqueous K2CO3 Solutions – SEM / EDX
DAY 7 DAY 21 DAY 28
Surface Coverage

30. Aqueous K2CO3 Solutions – SEM / EDX
DAY 7
Passivation layer
Epoxy Resin
Steel Coupon
Element Moles Ratio
C 16.11
O 44.98
Fe 38.91

31. Aqueous K2CO3 Solutions – SEM / EDX
DAY 7
Epoxy Resin
Steel Coupon
Element Moles Ratio
C 16.11
O 44.98
Fe 38.91
DAY 21

32. Aqueous MDEA Solutions – SEM / EDX
DAY 7
100% Surface Coverage
Element Mole Ratio
C 18.92
O 54.07
Fe 26.52
Suggests FeCO3

33. Aqueous AEP Solutions – SEM / EDX
DAY 7 DAY 28

34. Aqueous AEP Solutions – SEM / EDX
DAY 7 DAY 28

35. Aqueous AEP Solutions – SEM / EDX
DAY 28
Element Mole Ratio
Mn 1.05
Fe 98.63

36. Aqueous AEP Solutions – SEM / EDX
Cross-Section at Day 28
Epoxy Resin
Steel Coupon
Element Mole Ratio
C 85.97
O 12.30
Fe 1.72
Element Mole Ratio
Fe 100
Element Mole Ratio
C 28.01
Fe 71.99

37. Aqueous DETA Solutions – SEM / EDX
DAY 7 DAY 28

38. Aqueous MEA Solutions – SEM / EDX
DAY 7
Non-uniformity
Element Mole Ratio
C 59.34
O 10.73
Fe 29.12
Other 0.81
Element Mole Ratio
C 7.85
Fe 92.15

39. Aqueous MEA Solutions – SEM / EDX
DAY 7 DAY 14 DAY 21
Element Mole Ratio
Mn 1.07
Fe 98.93
Element Mole Ratio
C 11.24
Fe 88.76
Element Mole Ratio
C 7.85
Fe 92.15

40. Summary of Binary Aqueous Amine Solutions
MEA MDEA DETA* AEP AMP K2CO3*
Hanging film C P C C P P
ICP – OES ? P C C ? P
SEM / EDX C P C C P P
Overall C P C C P P
Corrosion Passivation
AEP DETA* MEA AMP MDEA K2CO3*

41. Conclusions
Traditional ‘hanging film’ method is an imprecise method for distinguishing
corrosion from passivation and determining the rate of change
Elemental analysis of both the solution and substrate provide strong
indicators of the corrosion and passivation occurring
Aqueous amine multi-component solutions can overcome the presence of
highly corrosive species
Rate of change observed on the substrate requires additional analysis
Corrosion Passivation
AEP DETA* MEA // AMP MDEA K2CO3*

42. Acknowledgements
This work is funded in part by the Department of Energy and Climate
Change and Carbon Clean Solutions.
Contributions to this work were made by: Miss Y. Zhao and Dr. J. Hall.

43. Understanding and addressing corrosion
due to amine solvents in post-combustion
carbon capture processes
KL Sedransk Campbell, DR Williams
Department of Chemical Engineering, Imperial College
UKCCSRC Biannual Meeting
April 21 2015