MATTRAN: Materials for Next Generation CO2 Pipeline Transport Systems - Julia race
The MATTRAN project explored materials for carbon dioxide transport systems, focusing on identifying corrosion and degradation issues to facilitate CO2 transport and carbon capture and storage (CCS). The findings include the development of new methods for analyzing CO2 mixtures and the effects of impurities on pipeline materials, demonstrating minimal stress corrosion cracking in various tested environments. The project produced valuable data and established a dynamic rig for testing materials under realistic CO2 transportation conditions.
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MATTRAN: Materials for Next Generation CO2 Pipeline Transport Systems - Julia race
- 1. Dr Julia Race2 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 OverallAim • 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 ProjectOverview 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 NextGeneration 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 Projectfindings 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 • Newdensity 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 NextGeneration 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 Projectfindings 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 CorrosionTest 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 testsperformed • 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 DrJulia 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 NextGeneration 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 fromplate 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 PolarisationCurve for Passive Film Forming Material Electrochemical Polarisation Cell Dr Julia Race 19 UKCCSRC Biannual Meeting 2nd-3rd April 2014
- 20. Results for DuplexStainless 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 DuplexStainless 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 316LStainless 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 316LStainless 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 316LStainless 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 X60Carbon 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 X60Carbon 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 Projectfindings 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 Projectfindings 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 StorageEOR 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 • Apipeline 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 • Someof 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 workhas 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 Race2 UKCCSRC Biannual Meeting 2nd-3rd April 2014