1. Dr Julia Race 2 UKCCSRC Biannual Meeting 2nd-3rd April 2014
Carbon Dioxide Transport
Infrastructure for the UK
Research Activities
at the
Newcastle University
MATTRAN
Materials for Next Generation Pipeline
Transportation: Findings on Impurities
UKCCSRC Biannual Meeting
2nd-3rd April 2014

2. MATTRAN Project Aims
Overall Aim
• to resolve the principal material issues required to allow the near
term implementation of CO2 transport, and thereby of CCS itself.
Sub-aims
• to define and predict the conditions under which corrosion,
degradation and internal cracking will occur;
• to validate the predictions with experimentation and modelling;
and
• to specify the material properties and/or CO2 stream composition
required to prevent or control corrosion, degradation, cracking
and fracture propagation.
Dr Julia Race
2
UKCCSRC Biannual Meeting
2nd-3rd April 2014

3. Project Overview
MATTRAN Project Overview
Project Timescale 46 months (October 2009 to July 2013)
Project Budget £1,543,874
Academic Institutions Involved Five
Co-investigators Eleven
Post Doctoral Research Associates Seven
PhD Students Four
Dr Julia Race
3
UKCCSRC Biannual Meeting
2nd-3rd April 2014

4. Materials for Next Generation CO2
Transport Systems (MATTRAN)
WP3: Pipeline
Specification
WP4: Internal Corrosion
& Degradation
Investigation
WP1: CO2 Stream
Specification
WP2: Phase & Dew
Point Determination
WP6: Fracture
Control
WP5: Internal Stress
Corrosion Cracking
Investigation
WP7: Synthesis
& Dissemination
Dr Julia Race
4
UKCCSRC Biannual Meeting
2nd-3rd April 2014

5. Key Findings
WP Project findings
WP1
The likely ranges of non-CO2 components from major industrial and power plant sources have been identified. This
work has updated the previous knowledge in this area and, in particular, allowed realistic experimental protocols to
be defined for testing in CO2 streams containing impurities.
WP2
A novel, numerically cheap equation of state has been produced that more accurately describes the phase and
density behaviours of CO2 mixtures.
Reliable methods for reproducibly making dilute mixtures of impurity gases in CO2 with well-defined compositions
have been developed.
The published database of densities of key CO2 binary and ternary mixtures as a function of temperature and
pressure and the boundary in temperature/pressure space between single and multiple phases in these mixtures
has been extended.
WP3
The effects that different impurities have on key aspects of pipeline design, operation, integrity and health and
safety have been investigated, and new requirements that need to be considered when specifying the maximum
levels of these impurities for entry into the pipeline system have been proposed.
A best practice for conducting hydraulic modelling using commercially available software has been proposed and
published. The hydraulic modelling approach developed in the MATTRAN programme has allowed the effect of
impurities on pipeline network design to be investigated.
Dr Julia Race
5
UKCCSRC Biannual Meeting
2nd-3rd April 2014

6. Phase Equilibrium & Solubility Test
Apparatus
Phase equilibrium test
equipment
Water solubility test equipment
Dr Julia Race
6
UKCCSRC Biannual Meeting
2nd-3rd April 2014

7. Database Extension
• New density data of key CO2 binary and ternary
mixtures (660 data points)
– CO2 + H2 (xH2 = 2%, 7.5% 10%)
– CO2 + N2 + H2 (xN2 = 5% and xH2 = 5%)
– 15 – 60 oC and pressures up 23 MPa (3300 psia)
• New phase equilibrium data of CO2 binary and ternary
mixtures (87 data points)
– CO2 + N2 (xH2 = 2%)
– CO2 + H2 (xH2 = 5%)
– CO2 + N2 + H2 (xN2 = 2% and xH2 = 3%)
– 0 – 30 oC
• New data of water solubility in CO2 with N2 as an impurity
– H2O + CO2 + N2 (xN2 = 5% and 10%)
– 25 and 40 oC
– pressures between 8 and 13 MPa (1200-2000 psia)
Dr Julia Race
7
UKCCSRC Biannual Meeting
2nd-3rd April 2014

8. Key Findings – Density
Measurements
• A concentration of only
2mol% of H2 in CO2 can
reduce the molar density
up to 25% in the critical
region.
• The effect of H2 on the
density of pure CO2 is
greater than that of N2.
Dr Julia Race
8
UKCCSRC Biannual Meeting
2nd-3rd April 2014

9. Key Findings – Phase Behaviour
• Compared with pure CO2,
the impurities (both N2
and H2) shift the phase
transition pressure to
much higher values.
• H2 increases significantly
the bubble-point pressure
at a given temperature.
Dr Julia Race
9
UKCCSRC Biannual Meeting
2nd-3rd April 2014

10. Key Findings – Water Solubility
• Addition of a small amount (10 mol %) of N2 in CO2
decreases the solubility of the water by 12-30% in the
pressure range of 8 - 13 MPa,
40 oC
Dr Julia Race
10
UKCCSRC Biannual Meeting
2nd-3rd April 2014

11. Materials for Next Generation CO2
Transport Systems (MATTRAN)
WP3: Pipeline
Specification
WP4: Internal Corrosion
& Degradation
Investigation
WP1: CO2 Stream
Specification
WP2: Phase & Dew
Point Determination
WP6: Fracture
Control
WP5: Internal Stress
Corrosion Cracking
Investigation
WP7: Synthesis
& Dissemination
Dr Julia Race
11
UKCCSRC Biannual Meeting
2nd-3rd April 2014

12. Key Findings
WP Project findings
WP4
A dense phase CO2 dynamic flow loop rig has been designed and built which can test materials in realistic
environments and operation conditions for CO2 transportation. This unique facility is now available for
further academic and industrial research.
The database of corrosion data for pipeline steels, stainless steels and polymers in binary CO2
environments with water has been extended to include CO2-SO2-H2O and CO2-H2S-H2O
WP5
A test protocol for slow strain rate testing of pipeline steels, stainless steel and duplex stainless steel has
been developed to allow the stress corrosion cracking testing of these steels in CO2-H2O environments in
combination with sulphur in the form sulphate, sulphite and sulphide. No stress corrosion cracking has been
observed in these environments for duplex stainless steel, 316 stainless steel or pipeline grade carbon
steels in any of the environmental conditions tested.
WP6
Based on the development of a unique fluid-structure interaction model backed by experimentation, this
study, for the first time, clearly demonstrates running brittle fractures as a highly plausible failure mode in
pressurised pipelines transporting CO2. The model has been applied to identify the range of operating
conditions, and the type of stream impurities that have the most impact on the susceptibility of the pipeline
to undergo brittle fracture.
WP7
The International Forum for the Transportation of CO2 by Pipeline, which ran annually between 2010 and
2013, has been established to disseminate information rapidly to the industry.
Dr Julia Race
12
UKCCSRC Biannual Meeting
2nd-3rd April 2014

13. Supercritical CO2 Corrosion Test
Apparatus
• Operates above 80 bar, 35oC (capable for up to 700
bar & -50 to 150 deg)
• Runs for several hundred hours depends on
material corrosion and environment
• Continuous monitoring of corrosion by electro
chemical noise & Linear Polarization Resistance
• Offline/online gas composition measurement
(infrared, mass spec)
• Includes several coupon geometry—plates, tubes,
bar, Charpy and tensile coupons
• Non-metallic materials degradation—seals,
lubricants
Dr Julia Race
13
UKCCSRC Biannual Meeting
2nd-3rd April 2014

14. Summary of tests performed
• Environments tested-2x1100 h exposure tests for
SO2 (500 ppm) and H2S (500 ppm) impurities. All
these environments saturated with water
• Exposed coupons for each environment, in total
30+ metallic coupons and 60+ non-metallic seals
Dr Julia Race
14
UKCCSRC Biannual Meeting
2nd-3rd April 2014

15. Corrosion data-SO2 environment
Dr Julia Race
15
UKCCSRC Biannual Meeting
2nd-3rd April 2014

16. Corrosion data - H2S environment
Dr Julia Race
16
UKCCSRC Biannual Meeting
2nd-3rd April 2014

17. Materials for Next Generation CO2
Transport Systems (MATTRAN)
WP3: Pipeline
Specification
WP4: Internal Corrosion
& Degradation
Investigation
WP1: CO2 Stream
Specification
WP2: Phase & Dew
Point Determination
WP6: Fracture
Control
WP5: Internal Stress
Corrosion Cracking
Investigation
WP7: Synthesis
& Dissemination
Dr Julia Race
17
UKCCSRC Biannual Meeting
2nd-3rd April 2014

18. Tensile specimen from plate
Slow strain rate
specimen
Test
solution
Closed glass
cell
Condenser
Top seal
Bottom seal
Heating
element
Slow strain rate
specimen
Test
solution
Closed glass
cell
Condenser
Top seal
Bottom seal
Heating
element
SSRT Configuration
Dr Julia Race
18
UKCCSRC Biannual Meeting
2nd-3rd April 2014

19. Electrochemical Testing
Typical Polarisation Curve for Passive Film Forming Material
Electrochemical Polarisation Cell
Dr Julia Race
19
UKCCSRC Biannual Meeting
2nd-3rd April 2014

20. Results for Duplex Stainless Steel
• Reducing the temperature or reducing the concentration can
reduce the severe corrosion
• No cracking was observed in any of the tests
Test Environment
Concentration
ppm
Temperature
degC
Potential
mV
UTS
MPa
YS
MPa
El
%
Ra
%
Time
min
Cracking Pitting Corrosion
D1 Air -- 18 -- 698.3 511.2 30.71 69 6306   
D8 Air -- 80 -- 674.2 463 32.4 71 5760   
D2 CO2 -- 80 -140 677.6 476.3 30.16 70 5724   
D3 CO2 + SO4 1000 40 -320 673 446.5 31.1 70 5880   
D4 CO2 + SO4 1000 80 -540 673.9 468.5 31.42 67 5802   
D5 CO2 + SO4 1000 80 -500 667.5 474.9 30.94 67 5844   
D6 CO2 + SO4 1000 80 -400 675.6 458.9 31.81 66 5976   
D11 CO2 + SO4 1000 80 600 701.1 484.4 34.3 67 6150   
D9 CO2 + SO4 1000 80 750 560.7 456.4 6.9 12 1920   
D15 CO2 + SO4 250 80 750 684.6 469.4 29.2 62 5400   
D16 CO2 + SO4 1000 40 750 673.3 511.2 30.4 59 5820   
CO2 + SO3 1000 40 -550 652.78 464.48 31.2 61 5820   
Test conditions Results
Dr Julia Race
20
UKCCSRC Biannual Meeting
2nd-3rd April 2014

21. Results for Duplex Stainless Steel
• Range of potentials (SCE)
tested from -500mV to
+750mV, potentials up to
+600mV saw no effect on
mechanical properties
• At +750mV large amount of
pitting and surface
corrosion of the material
occurs
Dr Julia Race
21
UKCCSRC Biannual Meeting
2nd-3rd April 2014

22. Results for 316L Stainless Steel
• Use linear polarisation sweeps to identify electrochemical potentials
(SCE) where cracking may occur in a given environment – Tap
water/CO2/1000ppm SO4
Dr Julia Race
22
UKCCSRC Biannual Meeting
2nd-3rd April 2014

23. Results for 316L Stainless Steel
• Use linear polarisation sweeps to identify electrochemical potentials
(SCE) where cracking may occur in a given environment – Tap
water/CO2/thiosulphate
Dr Julia Race
23
UKCCSRC Biannual Meeting
2nd-3rd April 2014

24. Results for 316L Stainless Steel
• No cracking observed in any of the environments tested
• Severe pitting experienced at 600mV in SO4 environment
and at 500mV in thiosulphate environment
Test Environment
Concentration
ppm
Temperature
degC
Potential
mV
UTS
MPa
YS
MPa
El
%
Ra
%
Time
min
Cracking Pitting Corrosion
S1 Air -- 18 -- 761.7 682.9 21.73 73 4728   
S6 Air -- 80 -- 723.7 678 18.7 74 3630   
CO2 -- 80 600 623.4 511 7.95 10 2100   
S2 CO2 + SO4 1000 80 -560 727.8 652.5 16.22 71 1722   
S3 CO2 + SO4 1000 80 -560 710 671.5 15.67 69 3264   
S4 CO2 + SO4 1000 80 -460 728.6 703.8 16.14 70 2034   
S7 CO2 + SO4 1000 80 500 717 600 19.3 70 3390   
S8 CO2 + SO4 1000 80 600 260.8 234.7 2 2 720   
S10 CO2 + SO4 1000 40 600 743 644 21.9 73 4200   
CO2 + thiosulphate 1000 80 -150 710.7 600 15.91 69 3330   
CO2 + thiosulphate 1000 80 100 722.3 643.5 16.93 70 3480   
CO2 + thiosulphate 1000 80 500 462.4 392.4 13.78 72 2400   
CO2 + CO
Test conditions Results
Dr Julia Race
24
UKCCSRC Biannual Meeting
2nd-3rd April 2014

25. Results for X60 Carbon Steel
• Comparison of electrochemical potentials (SCE) for – tap
water/CO2/1000ppm SO4 , tap water/CO2/1000ppm SO3,tap
water/CO2/CO
Dr Julia Race
25
UKCCSRC Biannual Meeting
2nd-3rd April 2014

26. Results for X60 Carbon Steel
• No cracking observed in any of the environments tested
• No passivation occurred on electrochemical testing in SO4
thiosulphate or CO environment
Test Environment
Concentration
ppm
Temperature
degC
Potential
mV
UTS
MPa
YS
MPa
El
%
Ra
%
Time
min
Cracking Pitting Corrosion
Air -- 80 -- 603.6 531.2 25.28 77 3720   
CO2 + SO4 1000 80 -600 520.2 483 12.99 70 2760   
CO2 + SO4 1000 80 -400 363.2 321.1 6.69 44 1590   
CO2 + thiosulphate
CO2 + CO
Test conditions Results
Dr Julia Race
26
UKCCSRC Biannual Meeting
2nd-3rd April 2014

27. Key Findings
WP Project findings
WP4
A dense phase CO2 dynamic flow loop rig has been designed and built which can test materials in realistic
environments and operation conditions for CO2 transportation. This unique facility is now available for
further academic and industrial research.
The database of corrosion data for pipeline steels, stainless steels and polymers in binary CO2
environments with water has been extended to include CO2-SO2-H2O and CO2-H2S-H2O
WP5
A test protocol for slow strain rate testing of pipeline steels, stainless steel and duplex stainless steel has
been developed to allow the stress corrosion cracking testing of these steels in CO2-H2O environments in
combination with sulphur in the form sulphate, sulphite and sulphide. No stress corrosion cracking has been
observed in these environments for duplex stainless steel, 316 stainless steel or pipeline grade carbon
steels in any of the environmental conditions tested.
WP6
Based on the development of a unique fluid-structure interaction model backed by experimentation, this
study, for the first time, clearly demonstrates running brittle fractures as a highly plausible failure mode in
pressurised pipelines transporting CO2. The model has been applied to identify the range of operating
conditions, and the type of stream impurities that have the most impact on the susceptibility of the pipeline
to undergo brittle fracture.
WP7
The International Forum for the Transportation of CO2 by Pipeline, which ran annually between 2010 and
2013, has been established to disseminate information rapidly to the industry.
Dr Julia Race
27
UKCCSRC Biannual Meeting
2nd-3rd April 2014

28. Key Findings
WP Project findings
WP1
The likely ranges of non-CO2 components from major industrial and power plant sources have been identified. This
work has updated the previous knowledge in this area and, in particular, allowed realistic experimental protocols to
be defined for testing in CO2 streams containing impurities.
WP2
A novel, numerically cheap equation of state has been produced that more accurately describes the phase and
density behaviours of CO2 mixtures.
Reliable methods for reproducibly making dilute mixtures of impurity gases in CO2 with well-defined compositions
have been developed.
The published database of densities of key CO2 binary and ternary mixtures as a function of temperature and
pressure and the boundary in temperature/pressure space between single and multiple phases in these mixtures
has been extended.
WP3
The effects that different impurities have on key aspects of pipeline design, operation, integrity and health and
safety have been investigated, and new requirements that need to be considered when specifying the maximum
levels of these impurities for entry into the pipeline system have been proposed.
A best practice for conducting hydraulic modelling using commercially available software has been proposed and
published. The hydraulic modelling approach developed in the MATTRAN programme has allowed the effect of
impurities on pipeline network design to be investigated.
Dr Julia Race
28
UKCCSRC Biannual Meeting
2nd-3rd April 2014

29. Projected Pipeline Specifications
DYNAMIS
ECOFYS
Storage EOR
CO2 >95% >95% >95%
H2O <500 ppm <500 ppm <500ppm
SOx <100 ppm <100 ppm Not critical
NOx <100 ppm <100 ppm Not critical
H2S <200 ppm <200 ppm <200ppm
CO <2000 ppm <2000 ppm <2000ppm
H2
Total non-
condensable
gases <4%vol
Total non-
condensable gases
<4%vol
Total non-
condensable gases
<4%vol
Ar
N2
O2 <100ppm
CH4 <100ppm
Dr Julia Race
29
UKCCSRC Biannual Meeting
2nd-3rd April 2014

30. MATTRAN Concluding Remarks
• At the time of funding, only integrated, inter-
disciplinary academic research programme in CO2
pipeline transportation in the UK
• Raised awareness of the requirement for CO2
transport research
• Still many under-researched areas being
highlighted in CO2 transport
• Requires teams of researchers working in a co-
ordinated manner
Dr Julia Race
30
UKCCSRC Biannual Meeting
2nd-3rd April 2014

31. Defining Specifications
• A pipeline specification must be considered in the
whole
• Pressure and temperature are also important in
defining pipeline specification
• For hydraulic analysis and fracture control:
– Specification driven by cost benefit analysis
– Limiting constraints determined by geometry and material
properties
• Specification of water critical in the specification of
NOx,, SOx, H2S, O2 and CO.
Dr Julia Race
31
UKCCSRC Biannual Meeting
2nd-3rd April 2014

32. Defining Specifications
• Some of the drivers have not been considered in
previous specifications e.g. fracture control and
sour corrosion and may drive the specification to
lower limits.
• A cautious approach to the specification of water
would seem prudent in initial stages
• The analysis conducted has indicated that there
are still some uncertainties in the specification
which require further investigation
Dr Julia Race
32
UKCCSRC Biannual Meeting
2nd-3rd April 2014

33. Acknowledgement
• This work has been conducted under the
auspices of the MATTRAN project (Materials for
Next Generation CO2 Transport Systems) and
the authors gratefully acknowledge the financial
support of EPSRC and E.ON for this research
(E.ON-EPSRC Grant Reference
EP/G061955/1).
Dr Julia Race
33
UKCCSRC Biannual Meeting
2nd-3rd April 2014

34. Dr Julia Race 2 UKCCSRC Biannual Meeting 2nd-3rd April 2014